P Pancreatin
P:0050
Synonyms: Beef viokase; Diastase vera; Donnazyme; Entozyme; Ilozyme; Intrazyme; Pancreatic extract; Pancrex-V; Pankreon; Pankrotanon; Panteric; Stamyl; Viobin; Viokase; Zypanar CAS Registry Number: 8057-43-0; 9002-16-8; 8049-47-6; 9046-39-3 RTECS® Number: RT9033000 Regulatory Authority and Advisory Bodies WGK (German Aquatic Hazard Class): No value assigned. Description: Pancreatin is a yellowish to cream-colored amorphous powder with a strong odor. Slightly soluble in water. Hazard Identification (based on NFPA-704 M Rating System): Health 1, Flammability 1, Reactivity 0. Potential Exposure: It is an enzyme found in the pancreas and is used in medicines and in treating leather and textiles. Incompatibilities: Alcohols, acids. Permissible Exposure Limits in Air No standards or TEEL available. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Pancreatin can affect you when breathed in. Exposure can cause an asthma-like lung reaction, with rapidly occurring symptoms of wheezing and shortness of breath. A second type of lung reaction, with fatigue, shortness of breath, and possibly fever, can occur hours after exposure. This can lead to scars in the lungs. Once allergy develops, even low exposures can trigger symptoms. Other proteolytic enzymes similar to Pancreatin can cause severe eye irritation and irritate the tongue, mouth, and cause nosebleeds and skin sores. Long Term Exposure: Repeated breathing exposure may cause changes in lung function, even without symptoms. May cause skin allergy, with rash and itching. May cause asthma-like allergy. Can cause severe allergic lung reaction with chills, fever, chest tightness, cough, and/or shortness of breath. Repeated attacks may lead to permanent lung scarring. Once allergy develops, even low exposures can trigger symptoms. Points of Attack: Lungs. Medical Surveillance: Before beginning employment and at regular times after that, for those with frequent or potentially high exposures, the following are recommended: lung function tests. These may be normal if the person is not having an attack at the time of the test. If symptoms develop or overexposure is suspected, the following may be useful: consider chest X-ray after acute overexposure. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, Sittig’s Handbook of Toxic and Hazardous Chemicals and Carcinogens. DOI: 10.1016/B978-1-4377-7869-4.00015-1
remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Medical observation for up to 8 h after breathing exposure is recommended, as symptoms may be delayed. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Where there is potential for exposure to pancreatin, use a NIOSH/MSHA- or European Standard EN149-approved full face-piece respirator with a highefficiency particulate filter. Greater protection is provided by a powered air-purifying respirator. Particulate filters must be checked every day before work for physical damage, such as rips or tears, and replaced as needed. Where there is potential for high exposures, use a NIOSH/MSHAor European Standard EN149-approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuous-flow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in pressure-demand or other positive-pressure mode. Storage: Color Code—Green: General storage may be used. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, well-ventilated area away from alcohol and acids. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations.
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© 2012 Richard Pohanish. Published by Elsevier Inc. All rights reserved.
Paraffin wax If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible solid but does not easily ignite. Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Poisonous gases are produced in fire. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Reference New Jersey Department of Health and Senior Services. (February 1987). Hazardous Substances Fact Sheet: Pancreatin. Trenton, NJ
Paraffin wax
P:0100
Molecular Formula: CnH2n 12 Synonyms: Hard paraffin; Paraffin; Paraffin, n-; Paraffin fume CAS Registry Number: 8002-74-2; 71808-29-2 (waxes, petroleum, clay-treated, reaction) RTECS® Number: RV0350000 UN/NA & ERG Number: Not regulated. EC Number: 232-315-6 Regulatory Authority and Advisory Bodies FDA—over-the-counter drug. US EPA TSCA Section 8(e) Risk Notification, 8EHQ0892-9311. Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. WGK (German Aquatic Hazard Class): Nonwater polluting agent. Description: Paraffin wax is a white, somewhat translucent solid and consists of a mixture of solid aliphatic hydrocarbons. It may be obtained from petroleum and consists of a mixture of high-molecular-weight hydrocarbons (e.g., C36H74). Specific gravity (H2O:1) 5 0.880.92; Freezing/ Melting point 5 4668 C; Flash point 5 198.9 C; Autoignition temperature 5 245 C. Hazard Identification (based on NFPA-704 M Rating System): Health 1, Flammability 0, Reactivity 1. Insoluble in water. Potential Exposure: Compound Description: Tumorigen, Primary Irritant. Paraffin is used in the manufacture of paraffin paper, candles, food package material, varnishes, floor
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polishes, and cosmetics. It is also used in waterproofing and extracting of essential oils from flowers for perfume. Incompatibilities: Strong oxidizers. Permissible Exposure Limits in Air Paraffin wax fume OSHA PEL: None. NIOSH REL: 2 mg/m3 TWA. ACGIH TLV®[1]: 2 mg/m3 TWA. Protective Action Criteria (PAC) 8002-74-2 TEEL-0: 2 mg/m3 PAC-1: 6 mg/m3 PAC-2: 100 mg/m3 PAC-3: 500 mg/m3 71808-29-2 TEEL-0: 10 mg/m3 PAC-1: 30 mg/m3 PAC-2: 50 mg/m3 PAC-3: 250 mg/m3 Australia: TWA 2 mg/m3 (fume), 1993; Belgium: TWA 2 mg/m3 (fume), 1993; Denmark: TWA 2 mg/m3 (fume), 1999; Finland: TWA 1 mg/m3 (fume), 1999; France: VME 2 mg/m3 (fume), 1999; Norway: TWA 2 mg/m3, 1999; Switzerland: MAK-W 2 mg/m3 (fume), 1999; the Netherlands: MAC-TGG 2 mg/m3, 2003; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: TWA 2 mg/m3. Several states have set guidelines or standards for paraffin wax fume in ambient air[60] ranging from 2060 μg/m3 (North Dakota) to 35 μg/m3 (Virginia) to 40 μg/m3 (Connecticut) to 48 μg/m3 (Nevada). Determination in Air: Use OSHA Analytical Method PV2047. Routes of Entry: Inhalation, eye contact. Harmful Effects and Symptoms Short Term Exposure: Irritates eyes and respiratory system. Inhalation can cause nausea. Occasionally sensitivity reactions have been reported. Chronic exposure can produce chronic dermatitis, wax boils, folliculitis, comedones, melanoderma, papules, and hyperkeratoses. Long Term Exposure: Fume can cause lung damage, and paraffins contain carcinogens. Carcinoma of the scrotum in pressmen exposed to crude petroleum wax has been documented. Other malignant lesions of an exposed area in employees working with finished paraffin are less well documented. Carcinoma of the scrotum, occurring in workmen exposed 10 years or more, began as a hyperkeratotic nevus like a lesion and developed into a squamous cell carcinoma. The lesions can metastasize to regional inguinal and pelvic lymph nodes. Paraffinoma has been reported from use of paraffin for cosmetic purposes. Summarize by calling it an equivocal tumorigenic agent. Points of Attack: Eyes, skin, respiratory system. Medical Surveillance: Medical examinations should be concerned especially with the skin. Surveillance should be continued indefinitely.
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Paraformaldehyde
First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in pressure-demand or other positive-pressure mode. Storage: Color Code—Green: General storage may be used. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, well-ventilated area away from oxidizers. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Ventilate area of spill or leak. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable.
Fire Extinguishing: Paraffin wax is a combustible solid. Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Poisonous gases are produced in fire. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Dissolve or mix the material with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber. All federal, state, and local environmental regulations must be observed. Reference Sax, N. I. (Ed.). (1981). Dangerous Properties of Industrial Materials Report, 1, No. 7, 6970
Paraformaldehyde
P:0120
Molecular Formula: (CH2O)x; C3H6O4 Synonyms: Aldacide; Flo-more; Formagene; Formaldehyde polymer; Granuform; Paraform; Paraform 3; Paraformaldehido (Spanish); Polyformaldehyde; Polymerized formaldehyde; Polyoxymethylene; Polyoxymethylene glycol; Triformol; Trioxymethylene CAS Registry Number: 30525-89-4; 110-88-3 (1,3,5trioxane) RTECS® Number: RV0540000 (paraformaldehyde); YM1400000 (trioxane) UN/NA & ERG Number: UN2213/133 EC Number: 203-812-5 [Annex I Index No.: 605-002-00-0] (1,3,5-trioxane) Regulatory Authority and Advisory Bodies Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. US EPA, FIFRA, 1998 Status of Pesticides: Supported. Clean Water Act: Section 311 Hazardous Substances/RQ 40CFR117.3 (same as CERCLA, see below). Reportable Quantity (RQ): 1000 lb (454 kg). Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations (110-88-3): Hazard Symbol: F, Xn; Risk phrases: R11, R37; R63; Safety phrases: S2; S36/37; S46 (see Appendix 4). WGK (German Aquatic Hazard Class): 2—Hazard to waters.
Paraformaldehyde Description: Paraformaldehyde is a white crystalline solid with an irritating odor. The term “trioxane” applies specifically to this trimer (CH2O)3, but paraformaldehyde is applied both to trioxane and other low polymers or oligomers of formaldehyde. Boiling point 5 115 C (trioxane); Freezing/Melting point 5 64 C (trioxane); 120180 C (decomposition/paraformaldehyde); Flash points 5 45 C (trioxane); 70 C (paraformaldehyde); Autoignition temperature 5 300 C. Explosive limits: LEL 5 3.6%; UEL 5 28.7% (trioxane); LEL 5 7.0%; UEL 5 73.0% (paraformaldehyde). Hazard Identification (based on NFPA704 M Rating System): Health 3, Flammability 3, Reactivity 1. Slightly soluble in water. Potential Exposure: Compound Description: Agricultural Chemical; Mutagen, Primary Irritant. Paraformaldehyde is used in polyacetal resin manufacture, as a food additive, and as an odorless fuel. Incompatibilities: Dust forms an explosive mixture with air. Decomposes on contact with oxidizers, strong acids, acid fumes, and bases; with elevated temperatures, forms formaldehyde. May explode when heated. May explode on impact if peroxide contamination develops. Mixtures with hydrogen peroxide or liquid oxygen are explosives sensitive to heat, shock, or contact with lead. Permissible Exposure Limits in Air Protective Action Criteria (PAC) TEEL-0: 4 mg/m3 PAC-1: 12.5 mg/m3 PAC-2: 75 mg/m3 PAC-3: 100 mg/m3 No TEEL available for trioxane. The Netherlands: 2 ppm/3 mg/m3 ceiling value[57]; Japan: 5 ppm TWA. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Exposure can irritate the eyes, nose, throat, and skin. Exposure can irritate the lungs, causing coughing and/or shortness of breath. Higher exposures can cause pulmonary edema, a medical emergency that can be delayed for several hours. This can cause death. See also “Formaldehyde”; this chemical forms formaldehyde when heated. Long Term Exposure: Repeated or prolonged contact may cause skin and lung sensitization, resulting in allergies. Paraformaldehyde may cause mutations. Handle with extreme caution. May cause kidney damage. Testing has not been completed to determine the carcinogenicity of paraformaldehyde. However, the limited studies to date indicate that these substances have chemical reactivity and mutagenicity similar to acetaldehyde and malonaldehyde. Therefore, NIOSH recommends that careful consideration should be given to reducing exposures to this aldehyde. Further information can be found in the NIOSH Current Intelligence Bulletin 55: Carcinogenicity of Acetaldehyde and Malonaldehyde, and Mutagenicity of Related
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Low-Molecular-Weight Aldehydes [DHHS (NIOSH), Publication No. 91-112]. Points of Attack: Lungs, kidneys, skin. Medical Surveillance: Before beginning employment and at regular times after that, for those with frequent or potentially high exposures, the following are recommended: lung function tests. These may be normal if person is not having an attack at the time. If symptoms develop or overexposure is suspected, the following may be useful: consider chest X-ray after acute overexposure. Evaluation by a qualified allergist, including careful exposure history and special testing, may help diagnose skin allergy. Kidney function tests. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 30 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Where there is potential for exposure to Paraformaldehyde, use a NIOSH/MSHA- or European Standard EN149-approved full face-piece respirator with a high-efficiency particulate filter. Greater protection is provided by a powered air-purifying respirator. Where there is potential for high exposures, use a NIOSH/MSHA- or European Standard EN149-approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuous-flow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in pressuredemand or other positive-pressure mode.
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Paraldehyde
Storage: Color Code—Red: Flammability Hazard: Store in a flammable materials storage area. Prior to working with this chemical you should be trained on its proper handling and storage. Before entering confined space where this chemical may be present, check to make sure that an explosive concentration is not a danger. Paraformaldehyde must be stored to avoid contact with oxidizers (such as perchlorates, peroxides, permanganates, chlorates, and nitrates), strong acids (such as hydrochloric, sulfuric, and nitric), and alkaline materials (such as potassium or sodium hydroxide), since violent reactions occur. Sources of ignition, such as smoking and open flames, are prohibited where paraformaldehyde is used, handled, or stored in a manner that could create a potential fire or explosion hazard. Protect containers from physical damage. Store in tightly closed containers in a cool, well-ventilated area away from areas of high humidity. Shipping: Paraformaldehyde requires a shipping label of “FLAMMABLE SOLID.” It falls in Hazard Class 4.1 and Packing Group III. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Establish forced ventilation to keep levels below explosive limit. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. Keep paraformaldehyde out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a flammable solid. Dust can form an explosive mixture with air. Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Poisonous gases are produced in fire, including formaldehyde. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Dissolve or mix the material with a combustible solvent and burn in a chemical
incinerator equipped with an afterburner and scrubber. All federal, state, and local environmental regulations must be observed. References Sax, N. I. (Ed.). (1983). Dangerous Properties of Industrial Materials Report, 3, No. 3, 9092 New Jersey Department of Health and Senior Services. (February 2000). Hazardous Substances Fact Sheet: Paraformaldehyde. Trenton, NJ
Paraldehyde
P:0130
Molecular Formula: C6H12O3 Common Formula: (CH3CHO)3 Synonyms: A13-03115; p-Acetaldehyde; Acetaldehyde, trimer; DEANo. 2585; Elaldehyde; NSC9799; Paraacetaldehyde; Paracetaldehyde; Paral; Paraldehido (Spanish); Paraldehyd (German); Paraldehyde draught; Paraldehyde enema; PCHO; Poral; Triacetaldehyde (French); 2,4,6-Trimethyl-1,3,5-trioxacyclohexane; 1,3,5-Trimethyl2,4,6-trioxane; 2,4,6-Trimethyl-s-trioxane; 2,4,6-Trimethyl1,3,5-trioxane; s-Trimethyltrioxymethylene; S-Trioxane, 2,4,6-trimethyl CAS Registry Number: 123-63-7 RTECS® Number: YK0525000 UN/NA & ERG Number: UN1264/129 EC Number: 204-639-8 [Annex I Index No.: 605-004-00-1] Regulatory Authority and Advisory Bodies Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. US EPA Hazardous Waste Number (RCRA No.): U182. RCRA, 40CFR261, Appendix 8 Hazardous Constituents. Reportable Quantity (RQ): 1000 lb (454 kg). EPCRA Section 313 Form R de minimis concentration reporting level: 1.0%. Canada, WHMIS, Ingredients Disclosure List Concentration 0.1%. European/International Regulations: Hazard Symbol: F; Risk phrases: R10; Safety phrases: S2; S29. (See Appendix 4). WGK (German Aquatic Hazard Class): 1—Low hazard to waters. Description: Paraldehyde is a colorless liquid with a pleasant odor. Molecular weight 5 132.18; Boiling point 5 125 C; Freezing/Melting point 5 12 C; Flash point 5 36 C; Autoignition temperature 5 237 C. Explosive Limits: LEL 5 1.3%; UEL — unknown. Hazard Identification (based on NFPA-704 M Rating System): Health 2, Flammability 3, Reactivity 1. Slightly soluble in water. Potential Exposure: Compound Description: Drug, Human Data; Primary Irritant. Paraldehyde is used primarily in medicine. It is used as a hypnotic agent, in delirium tremens, and in treatment of psychiatric states characterized by excitement when drugs given over a long period of time. It is also administered for intractable pain which
Paraldehyde does not respond to opiates and for basal and obstetrical anesthesia. It is effective against experimentally induced convulsions and has been used in emergency therapy of tetanus, eclampsia, status epilepticus, and poisoning by convulsant drugs. Since it is used primarily in medicine, the chance of accidental human exposure or environmental contamination is low. However, paraldehyde decomposes to acetaldehyde and acetic acid; these compounds have been found to be toxic. In this case, occupational exposure or environmental contamination is possible. Since paraldehyde is prepared from acetaldehyde by polymerization in the presence of an acid catalyst, there exists a potential for adverse effects, although none have been reported in the available literature. It is also used in the manufacture of organic compounds. Incompatibilities: Forms explosive mixture with air. Incompatible with strong oxidants, strong acids, alkalis, ammonia, amines, iodides, hydrocyanic acid. Violent reaction with liquid oxygen. Contact with acids form acetaldehyde. Attacks rubber and plastics. Permissible Exposure Limits in Air Protective Action Criteria (PAC) TEEL-0: 15 mg/m3 PAC-1: 40 mg/m3 PAC-2: 300 mg/m3 PAC-3: 300 mg/m3 Russia[43] set a MAC of 5.0 mg/m3 in work-place air. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Paraldehyde can affect you when breathed in and by passing through your skin. Contact can cause severe eye irritation or burns with possible permanent damage, and irritates the skin. Overexposure can cause poor coordination and make you sleepy. Higher exposures can cause pulmonary edema, a medical emergency that can be delayed for several hours. This can cause death. Long Term Exposure: High or repeated exposure can damage the liver and kidneys. Can irritate the lungs; bronchitis may develop. Repeated exposure may cause fatigue, tremors, changes in speech, personality changes, and/or poor memory. Points of Attack: Liver, kidneys, lungs, brain. Medical Surveillance: Liver and kidney function tests. Examine for brain effects. Consider chest X-ray following acute overexposure. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical
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facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Where there is potential for exposures to paraldehyde, use a NIOSH/MSHA- or European Standard EN149-approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuous-flow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in pressure-demand or other positive-pressure mode. Storage: Color Code—Red: Flammability Hazard: Store in a flammable liquid storage area or approved cabinet away from ignition sources and corrosive and reactive materials. Prior to working with this chemical you should be trained on its proper handling and storage. Before entering confined space where this chemical may be present, check to make sure that an explosive concentration is not a danger. Paraldehyde must be stored to avoid contact with oxidizers (such as perchlorates, peroxides, permanganates, chlorates, and nitrates), liquid oxygen, alkalis, and nitric acid, since violent reactions occur. Store in tightly closed containers in a cool, well-ventilated area. Sources of ignition, such as smoking and open flames, are prohibited where paraldehyde is handled, used, or stored. Metal containers involving the transfer of 5 gallons or more of paraldehyde should be grounded and bonded. Drums must be equipped with selfclosing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of paraldehyde. Shipping: This compound requires a shipping label of “FLAMMABLE LIQUID.” It falls in Hazard Class 3 and Packing Group II. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Establish forced ventilation to keep levels below explosive limit. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a
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Paraoxon
similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a flammable liquid. Poisonous gases, including formaldehyde, are produced in fire. Use dry chemical, carbon dioxide, alcohol foam, or polymer foam extinguishers. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Incineration in added solvent. Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant ($100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. References US Environmental Protection Agency. (April 30, 1980). Paraldehyde, Health and Environmental Effects Profile No. 140. Washington, DC: Office of Solid Waste Sax, N. I. (Ed.). Dangerous Properties of Industrial Materials Report, 5, No. 6, 8790 (1985) and 8, No. 6, 7479 (1988) New Jersey Department of Health and Senior Services. (January 2000). Hazardous Substances Fact Sheet: Paraldehyde. Trenton, NJ
Paraoxon
P:0140
Molecular Formula: C10H14NO6P Synonyms: Chinorta; Diaethyl-p-nitrophenylphosphorsaeureester (German); O,O0 -Diethyl-p-nitrophenylphosphat
(German); O,O-Diethyl O,p-nitrophenyl phosphate; O,ODiethyl p-nitrophenyl phosphate; Diethyl-p-nitrophenyl phosphate; Diethyl paraoxon; O,O-Diethylphosphoric acid O, p-nitrophenyl ester; E 600; ENT16,087; Ester 25; Ethyl-pnitrophenyl ethylphosphate; Ethyl paraoxon; Eticol; Fosfakol; HC2072; Mintaco; Mintacol; Miotisal; Miotisal A; O,p-Nitrofenilfosfato de O,O-dietilo (Spanish); p-Nitrophenyl diethylphosphate; Oxyparathion; Paraoxone; Paroxan; Pestox 101; Phosphacol; Phosphoric acid, diethyl p-nitrophenyl ester; Phosphoric acid, diethyl 4-nitrophenyl ester; Soluglacit; TS219 CAS Registry Number: 311-45-5 RTECS® Number: TC2275000 UN/NA & ERG Number: UN3278 (organophosphorus compound, toxic n.o.s.)/151 EC Number: 206-221-0 Regulatory Authority and Advisory Bodies US EPA Hazardous Waste Number (RCRA No.): P041. RCRA, 40CFR261, Appendix 8 Hazardous Constituents. Reportable Quantity (RQ): 100 lb (45.4 kg). US DOT Regulated Marine Pollutant (49CFR172.101, Appendix B). US DOT 49CFR172.101, Inhalation Hazard Chemical as organophosphates. European/International Regulations: Hazard Symbol: T 1 , N; Risk phrases: R27/28; R50/53; Safety phrases: S1/2; S28; S36/37; S45; S60; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): No value assigned. Description: Paraoxon is an odorless, reddish-yellow oil. Molecular weight 5 275.22; Boiling point 5 170 C at 1 mmHg; Freezing/Melting point 5 189 C; Vapor 25 pressure 5 9 3 10 mmHg at 25 C. Slightly soluble in water; solubility 5 3640 mg/L at 20 C. Potential Exposure: An organophosphate insecticide. It has been used as a medication. Incompatibilities: Decomposes in alkaline materials. Permissible Exposure Limits in Air No standards or TEEL available. This chemical can be absorbed through the skin, thereby increasing exposure. Determination in Air: Use NIOSH Analytical Method (IV) Method #5600, Organophosphorus Pesticides. Determination in Water: Octanolwater coefficient: Log Kow 5 1.59. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Can cause rapid organophosphate poisoning. Organic phosphorus insecticides are absorbed by the skin as well as by the respiratory and gastrointestinal tracts. They are cholinesterase inhibitors. Symptoms of exposure include headache, giddiness, blurred vision, nervousness, weakness, nausea, cramps, diarrhea, and discomfort in the chest. Signs include sweating, tearing, salivation, vomiting, cyanosis, convulsions, coma, loss of reflexes, and loss of sphincter control. LD50 5 (oral-rat) 1.8 mg/kg.
Paraoxon Long Term Exposure: Cholinesterase inhibitor; cumulative effect is possible. This chemical may damage the nervous system with repeated exposure, resulting in convulsions, respiratory failure. Repeated exposure may cause personality changes, including depression, anxiety, irritability. May cause liver damage. Points of Attack: Respiratory system, lungs, central nervous system, cardiovascular system, skin, eyes, plasma and red blood cell cholinesterase. Medical Surveillance: Before employment and at regular times after that, the following are recommended: plasma and red blood cell cholinesterase levels (tests for the enzyme poisoned by this chemical). If exposure stops, plasma levels return to normal in 12 weeks while red blood cell levels may be reduced for 13 months. When cholinesterase enzyme levels are reduced by 25% or more below preemployment levels, risk of poisoning is increased, even if results are in lower ranges of “normal.” Reassignment to work not involving organophosphate or carbamate pesticides is recommended until enzyme levels recover. If symptoms develop or overexposure occurs, repeat the above tests as soon as possible and get an examination of the nervous system. Also, consider complete blood count. Consider chest X-ray following acute overexposure. Do not drink any alcoholic beverages before or during use. Alcohol promotes absorption of organic phosphates. Refer to the NIOSH Criteria Documents #78174 and #76-147 on manufacturing, formulating, and working safely with pesticides. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Speed in removing material from skin is of extreme importance. Shampoo hair promptly if contaminated. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash.
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Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in pressure-demand or other positive-pressure mode. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, wellventilated area away from strong oxidizers. Where possible, automatically transfer material from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of this chemical should be grounded and bonded. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: Organophosphorus compound, toxic n.o.s. require a shipping label of “POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 6.1. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Ventilate area of spill or leak. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Initial isolation and protective action distances: Distances shown are likely to be affected during the first 30 min after materials are spilled and could increase with time. If more than one tank car, cargo tank, portable tank, or large cylinder involved in the incident is leaking, the protective action distance may need to be increased. You may need to seek emergency information from CHEMTREC at (800) 4249300 or seek professional environmental engineering assistance from the US EPA Environmental Response Team at (908) 548-8730 (24-h response line). Small spills (From a small package or a small leak from a large package) First: Isolate in all directions (feet/meters) 100/30 Then: Protect persons downwind (miles/kilometers)
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Paraquat (paraquat dichloride)
Day 0.3/0.4 Night 0.8/1.2 Large spills (From a large package or from many small packages) First: Isolate in all directions (feet/meters) 600/200 Then: Protect persons downwind (miles/kilometers) Day 1.6/2.6 Night 2.8/4.5 Fire Extinguishing: This chemical is a combustible liquid, but does not readily ignite. Poisonous gases, including oxides of phosphorus and nitrogen, are produced in fire. Use dry chemical, carbon dioxide, or alcohol foam extinguishers. Vapors are heavier than air and will collect in low areas. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: In accordance with 40CFR165, follow recommendations for the disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by contacting your local or federal environmental control agency or by contacting your regional EPA office. Reference New Jersey Department of Health and Senior Services. (May 2000). Hazardous Substances Fact Sheet: Paraoxon. Trenton, NJ
Paraquat (paraquat dichloride)P:0150 Molecular Formula: C12H14Cl2N2 Common Formula: C12H14N2Cl2 Synonyms: AH 501; AI3-61943; 4,40 -Bipyridinium, 1,10 dimethyl-, dichloride; Bipyridinium, 1,10 -dimethyl-4,40 -, dichloride; Cekuquat; para-COL; Crisquat; Dextrone; Dextrone-X; N,N0 -Dimethyl-4,40 -bipyridinium dichloride; 1,10 -Dimethyl-4, 40 -bipyridinium dichloride; N,N0 0 0 Dimethyl-4,4 -bipyridylium dichloride; 1,1 -Dimethyl-4,40 bipyridynium dichloride; 1,1-Dimethyl-4,4-dipyridilium dichloride; 4,40 -Dimethyldipyridyl dichloride; 1,10 0 0 Dimethyl-4,4 -dipyridylium chloride; N,N -Dimethyl-4,40 dipyridylium dichloride; 1,10 -Dimethyl-4,40 -dipyridylium
dichloride; Dimethyl violgen chloride; Dimethyl viologen chloride; Esgram; Gamixel; Goldquat 276; Gramoxone; Gramoxone D; Gramoxone dichloride; Gramoxone S; Gramoxone W; Herboxone; Methyl viologen; Methyl viologen (reduced); Methyl viologen chloride; Methyl viologen dichloride; NSC263500; NSC 88126; OK622; Paraquat chloride; ortho-Paraquat Cl; Paraquat Cl; Paraquat dichloride; Paraquat dichloride bipyridylnium herbicide; Pathclear; Pillarquat; Pillarxone; PP 148; Sweep; Terraklene; Toxer total; Viologen, methyl-; Weedol Note: Paraquat is a cation (C12H14N2 11 ; 1,1-Dimethyl4,4-bipyridinium ion); the commercial product is the dichloride salt of paraquat.[NIOSH] CAS Registry Number: 4685-14-7 (cation); 1910-42-5 (dichloride); (alt.) 3765-78-4; (alt.) 57593-74-5; (alt.) 65982-50-5; (alt.) 136338-65-3; (alt.) 205105-68-6; (alt.) 247050-57-3; 4032-26-2 (diiodide); 2074-50-2 (dimethylsulfate; methosulfat) RTECS® Number: DW1960000 (cation); DW2275000 (dichloride); DW2280000 (diiodide); DW2010000 (dimethylsulfate) UN/NA & ERG Number: UN2781 EC Number: 225-141-7; 217-615-7 [Annex I Index No.: 613-090-00-7]; 223-714-6 [Annex I Index No.: 613-089-001] (diquat dichloride); 218-196-3 [Annex I Index No.: 613090-00-7] (paraquat-dimethylsulfate) Regulatory Authority and Advisory Bodies Carcinogenicity: EPA (dichloride): Possible Human Carcinogen. US EPA Gene-Tox Program, Positive: S. cerevisiae gene conversion. US EPA, FIFRA 1998 Status of Pesticides: RED completed. Banned or Severely Restricted (several countries) (UN).[13] Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. SUPERFUND/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 100/10,000 lb (45.4/4540 kg) (dichloride). Reportable Quantity (RQ): 10 lb (4.54 kg) (dichloride). EPCRA Section 313 Form R de minimis concentration reporting level: 1.0%. European/International Regulations (dichloride): Hazard Symbol: T, N; Risk phrases: R24/25; R26; R36/37/38; R48/ 25; R50/53; Safety phrases: S1/2; S22; S28; S36/37/39; S45; S60; 61 (see Appendix 4). WGK (German Aquatic Hazard Class): No value assigned. Description: Paraquat is a yellow solid with a faint, ammonia-like odor. Molecular weight 5 186.28; Specific gravity (H2O:1) 5 1.25; Boiling point 5 decomposes; Freezing/ Melting point 5 298 C (decomposes). Hazard Identification (based on NFPA-704 M Rating System): (paraquat) Health 4, Flammability 0, Reactivity 0. Soluble in water. Paraquat dichloride is a quaternary ion which is usually used as the dichloride salt. Molecular weight 5 257.18. Highly soluble in water.
Paraquat (paraquat dichloride) Potential Exposure: Compound Description: Agricultural Chemical; Drug, Mutagen; Reproductive Effector; Human Data; Primary Irritant. Those engaged in the manufacture, formulation, and application of this herbicide. Classified for restricted use: limited to use by a certified applicator, or those under applicator’s direct supervision. Incompatibilities: Strong oxidizers, alkylaryl-sulfonate wetting agents; strong bases (hydrolysis). Corrosive to metals. Decomposes in the presence of ultraviolet light. Decomposes in heat (see physical properties, above) and in the presence of UV light, producing nitrogen oxides, hydrogen chloride. Permissible Exposure Limits in Air OSHA PEL (cation, dichloride, methosulfate): 0.5 mg/m3 respirable dust TWA [skin]. NIOSH REL (dichloride): 0.1 mg/m3 respirable fraction TWA [skin]. ACGIH TLV®[1] (cation): 0.5 mg/m3/; 0.1 mg/m3 respirable fraction TWA. NIOSH IDLH: 1 mg/m3. Protective Action Criteria (PAC) (dichloride) TEEL-0: 0.1 mg/m3 PAC-1: 0.1 mg/m3 PAC-2: 0.15 mg/m3 PAC-3: 1 mg/m3 4685-14-7 TEEL-0: 0.1 mg/m3 PAC-1: 0.25 mg/m3 PAC-2: 1 mg/m3 PAC-3: 1 mg/m3 DFG MAK (dichloride): 0.1 mg/m3 measured as the inhalable fraction TWA; Peak Limitation Category I(1); [skin]. Austria: MAK 0.1 mg/m3, [skin], 1999; Denmark: TWA 0.1 mg/m3, [skin], 1999; Switzerland: MAK-W 0.1 mg/m3, KZG-W 0.2 mg/m3, [skin], 1999; United Kingdom: TWA 0.08 mg/m3, respirable dust, 2000; the Netherlands: MACTGG 0.1 mg/m3, 2003; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: TWA 0.5 mg/m3. Several states have set guidelines or standards for paraquat in ambient air[60] ranging from 0.33 μg/m3 (New York) to 0.50 μg/m3 (South Carolina) to 1.0 μg/m3 (Florida) to 1.6 μg/m3 (Virginia) to 2.0 μg/m3 (Connecticut and Nevada). Determination in Air: Use NIOSH Analytical Method (IV) #5003, Paraquat. Permissible Concentration in Water: A lifetime health advisory of 3.0 μg/L has been derived by EPA (See “References” Below). In addition, the state of Maine[61] has set a guideline of 17.0 μg/L for paraquat in drinking water. Determination in Water: Fish Tox 5 2115.13304000 ppb (VERY LOW); Octanolwater coefficient: Log Kow 5 24.2. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Absorbed through the skin. Harmful Effects and Symptoms Short Term Exposure: Irritates the eyes, skin, and respiratory tract. Inhalation can cause pulmonary edema, a medical
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emergency that can be delayed for several hours. This can cause death. Effects occur in two stages, immediate and delayed. Caution is advised. Exposure to paraquat may be fatal; there is no effective antidote. Signs and symptoms of acute exposure to paraquat may be severe and include nausea, vomiting, diarrhea, and abdominal pain. A burning sensation of the mouth and esophagus with possible ulceration may occur following ingestion. Eye exposure may result in corneal opacification (cloudiness). Dermatitis and nail atrophy may occur following dermal contact. Delayed effects include transient reversible liver injury, acute renal failure, and progressive pulmonary fibrosis with associated dyspnea (shortness of breath) and pulmonary edema. Absorbed through the skin and can lead to symptoms as listed in the following paragraph. In addition, can cause fingernail discoloration and damage (which returns to normal when exposure stops), irritation, redness, swelling, and burning. Exposure through ingestion may cause burning of the mouth and throat, nausea, vomiting, abdominal pain, diarrhea, and damage to the kidneys, heart, and liver. Lung damage, leading to death, may occur. One-half ounce of a 20% solution has caused death. Ingestion can also cause lung hemorrhage and fibrosis. The substance may cause effects on the lungs, kidneys, liver, cardiovascular system, and gastrointestinal tract, resulting in impaired functions, tissue lesions. Long Term Exposure: Repeated or prolonged contact with skin may cause damage and possible loss of the fingernails, and can lead to dry and cracking skin with blistering. Repeated or prolonged exposure to the aerosol can cause lung irritation, lung damage; bronchitis may develop. Can cause scarring of the lungs leading to breathlessness. Can damage the liver, kidneys, and affect the heart. Human Tox 5 3.15000 ppb Health Advisory (HIGH). Points of Attack: Eyes, skin, respiratory system, heart, liver, kidneys, gastrointestinal tract. Medical Surveillance: NIOSH lists the following tests: chest X-ray; liver function tests; pulmonary function tests: forced vital capacity, forced expiratory volume (1s); urine (chemical/metabolite); urinalysis (routine). Consider the points of attack in preplacement and periodic physical examinations. Kidney function tests. EKG. Chemical users should be cautioned about the use of alcohol which can increase liver damage. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water, or bentonite
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Paraquat (paraquat dichloride)
clay in water, or activated charcoal in water; and induce vomiting. Do not make an unconscious person vomit. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. Obtain authorization and/or further instructions from the local hospital for performance of other invasive procedures. Rush to a health-care facility. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: NIOSH: Up to 1 mg/m3: CcrOv95* (APF 5 10) [any air-purifying half-mask respirator with organic vapor cartridge(s) in combination with an N95, R95, or P95 filter. The following filters may also be used: N99, R99, P99, N100, R100, P100]; or PaprOvHie* (APF 5 25) (any powered air-purifying respirator with an organic vapor cartridge in combination with a highefficiency particulate filter); or Sa* (APF 5 10) (any supplied-air respirator); or SCBAF (APF 5 50) (any selfcontained breathing apparatus with a full face-piece). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd,Pp (APF 5 10,000) (any NIOSH/MSHA- or European Standard EN 149-approved self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positivepressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary, self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: GmFOv100 (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or back-mounted organic vapor canister having an N100, R100, or P100 filter] or SCBAE (any appropriate escape-type, self-contained breathing apparatus). *Substance reported to cause eye irritation or damage; may require eye protection. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. This chemical is inactivated by inert clays and anionic surfactants. Store in tightly closed containers in a cool, well-ventilated area away from oxidizers, alkylarylsulfonate wetting agents, light. Where possible, automatically pump material from drums or other storage containers
to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of this chemical should be grounded and bonded. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: Bipyridilium pesticides, solid, toxic, require a shipping label of “POISONOUS/TOXIC MATERIALS.” They fall in DOT Hazard Class 6.1 and Paraquat is in Packing Group II. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Poisonous gases, including nitrogen oxides, are produced in fire. Remove all ignition sources. Stay upwind; keep out of low areas. Ventilate closed spaces before entering them. Remove and isolate contaminated clothing at the site. If water pollution occurs, notify appropriate authorities. Do not touch spilled material; stop leak if you can do so without risk. Use water spray to reduce vapors. Small spills: absorb with sand or other noncombustible absorbent material and place into containers for later disposal. Small dry spills: with clean shovel place material into clean, dry container and cover; move containers from spill area. Large spills: dike far ahead of spill for later disposal. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible solid. Procedures for bipyridilium pesticides are as follows. Small fires: dry chemical, carbon dioxide, water spray, or foam. Large fires: water spray, fog, or foam. Move container from fire area if you can do so without risk. Fight fire from maximum distance. Dike fire control water for later disposal; do not scatter the material. Poisonous gases are produced in fire. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. Containers may explode in fire. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Paraquat is rapidly inactivated in soil. It is also inactivated by anionic surfactants.
Paraquat methosulfate Therefore, an effective and environmentally safe disposal method would be to mix the product with ordinary household detergent and bury the mixture in clay soil. In accordance with 40CFR165, follow recommendations for the disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by contacting your local or federal environmental control agency or by contacting your regional EPA office. Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant ($100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. References Pasi, A. (1978). The Toxicology of Paraquat, Diquat and Morfamquat. Bern, Switzerland: H. Huber US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Paraquat. Washington, DC: Chemical Emergency Preparedness Program Sax, N. I. (Ed.). (1988). Dangerous Properties of Industrial Materials Report, 8, No. 2, 6772 US Environmental Protection Agency. (August 1987). Health Advisory: Paraquat. Washington, DC: Office of Drinking Water New York State Department of Health. (February 1986). Chemical Fact Sheet: Paraquat (Version 2 and Version 3). Albany, NY: Bureau of Toxic Substance Assessment New Jersey Department of Health and Senior Services. (September 1999). Hazardous Substances Fact Sheet: Paraquat. Trenton, NJ US Environmental Protection Agency, Special Review and Reregistration Division Office of Pesticide Programs. (1998). Agency Status of Pesticides in Registration, Reregistration, and Special Review (Rainbow Report). Washington, DC
Paraquat methosulfate
P:0160
Molecular Formula: C14H20N2O8S2 Common Formula: C12H14N2(CH3SO4)2 Synonyms: 4,4-Bipyridinium, 1,10 -dimethyl-, bis(methyl sulfate); 1,10 -Dimethyl-4,40 -bipyridyniumdimethylsulfate; 1,10 -Dimethyl-4,40 -dipyridynium di(methyl sulfate); Gramoxone methyl sulfate; Paraqiat I; Paraquat bis(methyl sulfate); Paraquat dimethosulfate; Paraquat dimethyl sulphate; Paraquat dimethyl sulfate; Paraquat methsulfate bipyridylnium herbicide; PP 910 CAS Registry Number: 2074-50-2 RTECS® Number: DW2010000 UN/NA & ERG Number: UN2781/151 EC Number: 218-196-3 [Annex I Index No.: 613-090-00-7] Regulatory Authority and Advisory Bodies Banned or Severely Restricted (Hungary) (UN).[13]
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SUPERFUND/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 10/10,000 lb (4.54/4540 kg). Reportable Quantity (RQ): 10 lb (4.54 kg). European/International Regulations (includes dichloride): Hazard Symbol: T, N; Risk phrases: R24/25; R26; R36/37/ 38; R48/25; R50/53; Safety phrases: S1/2; S22; S28; S36/ 37/39; S45; S60; 61 (see Appendix 4). WGK (German Aquatic Hazard Class): No value assigned. Description: Paraquat methosulfate is a white to yellow crystalline solid. Molecular weight 5 408.48; Freezing/ Melting point 5 175180 C (decomposition). Hazard Identification (based on NFPA-704 M Rating System): Health 4, Flammability 0, Reactivity 0. Soluble in water. Potential Exposure: Those who might be involved in the manufacture or use of this contact herbicide and desiccant. Incompatibilities: Strong oxidizers. Permissible Exposure Limits in Air Protective Action Criteria (PAC) TEEL-0: 0.75 mg/m3 PAC-1: 2 mg/m3 PAC-2: 15 mg/m3 PAC-3: 40 mg/m3 A MAC of 0.01 mg/m3 has been set in Bulgaria according to the EPA Profile (see “References,” below). Determination in Air: Use NIOSH Analytical Method (IV) #5003, Paraquat. Permissible Concentration in Water: Paraquat: A lifetime health advisory of 3.0 μg/L has been derived by EPA (see “References,” below). In addition, the state of Maine[61] has set a guideline of 17.0 μg/L for paraquat in drinking water. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Contact causes irritation. Inhalation causes nosebleeds, headaches, coughing, and a sore throat. Higher exposures can cause pulmonary edema, a medical emergency that can be delayed for several hours. This can cause death. Swallowing causes burning in mouth, throat, and abdomen; vomiting, bloody vomitus; diarrhea with bloody stools; and headaches. It can cause death by shock and/or pulmonary damage. The fatal dose is estimated to be 6 g of paraquat ion. Exposure may cause renal tubular damage and liver dysfunction. Death may occur in 24 h or less. Long Term Exposure: Liver and kidney damage. Points of Attack: Lungs, liver, kidneys. Medical Surveillance: NIOSH lists the following tests (paraquat dichloride): chest X-ray; liver function tests; pulmonary function tests: forced vital capacity, forced expiratory volume (1 s); urine (chemical/metabolite); urinalysis (routine). First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately.
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Paraquat methosulfate
If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in pressure-demand or other positive-pressure mode. The following is for reference: NIOSH (for paraquat dichloride): Up to 1 mg/m3: CcrOv95* (APF 5 10) [any airpurifying half-mask respirator equipped with an organic vapor cartridge(s) in combination with an N95, R95, or P95 filter. The following filters may also be used: N99, R99, P99, N100, R100, P100]; or PaprOvHie* (APF 5 25) (any powered air-purifying respirator with an organic vapor cartridge in combination with a high-efficiency particulate filter); or Sa* (APF 5 10) (any supplied-air respirator); or SCBAF (APF 5 50) (any self-contained breathing apparatus with a full face-piece). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd, Pp (APF 5 10,000) (any NIOSH/MSHA- or European Standard EN 149-approved self-contained breathing apparatus that has a full face-piece and is operated in a pressuredemand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary, self-contained breathing apparatus operated in a pressure-demand or other positive pressure mode). Escape: GmFOv100 (APF 5 50) [any air-purifying, full-face-piece
respirator (gas mask) with a chin-style, front- or backmounted organic vapor canister having an N100, R100, or P100 filter] or SCBAE (any appropriate escape-type, selfcontained breathing apparatus). *Substance reported to cause eye irritation or damage; may require eye protection. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, wellventilated area away from oxidizers. Where possible, automatically transfer material from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of this chemical should be grounded and bonded. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: Bipyridilium pesticides, solid, toxic, require a shipping label of “POISONOUS/TOXIC MATERIALS.” They fall in DOT Hazard Class 6.1 and Paraquat is in Packing Group III. Spill Handling: Remove all ignition sources. Keep unnecessary people away; isolate hazard area and deny entry. Stay upwind; keep out of low areas. Do not touch spilled material; stop leak if you can do so without risk. Small spills: absorb with sand or other noncombustible absorbent material and place into containers for later disposal. Small dry spills: with clean shovel place material into clean, dry container and cover; move containers from spill area. Large spills: dike far ahead of spill for later disposal. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a noncombustible solid. Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Poisonous gases are produced in fire, including nitrogen oxides and sulfur oxides. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for
Parathion firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: In accordance with 40CFR165, follow recommendations for the disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by contacting your local or federal environmental control agency or by contacting your regional EPA office. Reference US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Paraquat Methosulfate. Washington, DC: Chemical Emergency Preparedness Program
Parathion
P:0170
Molecular Formula: C10H14NO5PS Synonyms: AAT; AATP; ACC 3422; Alkron; Alleron; American cyanamid 3422; Aphamite; Aralo; B 404; BAY E-605; Bayer E-605; Bladan F; Compound 3422; Corothion; Corthion; Corthione; Danthion; O,O-Diethyl O(p-nitrophenyl) phosphorothioate; O,O-Diethyl O-(4-nitrophenyl) phosphorothioate; O,O-Diethyl O,p-nitrophenyl phosphorothioate; Diethyl p-nitrophenyl phosphorothionate; Diethyl 4-nitrophenyl phosphorothionate; Diethyl p-nitrophenyl thionophosphate; O,O-Diethyl O,p-nitrophenyl thiophosphate; Diethyl parathion; DNTP:; DPP; Drexel parathion 8E; E 605; E 605 F; Ecatox; Ekatin WF & WF ULV; Ekatox; ENT15,108; Ethlon; Ethyl parathion; Etilon; Folidol; Folidol E; Folidol E-605; Folidol E&E 605; Folidol oil; Fosfermo; Fosferno; Fosfex; Fosfive; Fosova; Fostern; Fostox; Gearphos; Genithion; Kalphos; Kypthion; Lethalaire G-54; Lirothion; Murfos; Murphos; NCIC00226; Niran; Niran E-4; Nitrostigmin (German); Nitrostigmine; NIUIF 100; Nourithion; Oleofos 20; Oleoparathene; Oleoparathion; OMS 19; Orthophos; PAC; Pacol; Panthion; Paradust; Paramar; Paramar 50; Paraphos; Parathene; Parathion-ethyl; Parathion thiophos; Parationa (Spanish); Parawet; Penncap E; Pestox plus; Pethion; Phoskil; Phosphorothioic acid, O,O-diethyl O-(p-nitrophenyl) ester; Phosphorothioic acid, O,O-diethyl O-(4-nitrophenyl) ester; Phosphostigmine; Pleoparaphene; RB; Rhodiasol; Rhodiatox; Rhodiatrox; Selephos; SNP; Soprathion; Stathion; STCC4921469; Sulphos; Super rodiatox; T-47; Thiomex; Thiophos; Thiophos 3422; Tiofos; TOX 47; Toxol (3); Vapophos; Vitrex CAS Registry Number: 56-38-2; (alt.) 8057-70-3; (alt.) 11111-91-4; (alt.) 110616-89-2 RTECS® Number: TF4550000 UN/NA & ERG Number: UN2783 (Methyl parathion, solid)/152; UN1967 (Parathion and compressed gas mixture)/123; UN3018 (organophosphorus pesticide, liquid, toxic)/152 EC Number: 200-271-7 [Annex I Index No.: 015-034-00-1]
2057
Regulatory Authority and Advisory Bodies Carcinogenicity: IARC: Animal Inadequate Evidence; Human No Adequate Data, not classifiable as carcinogenic to humans, Group 3, 1987; EPA: Possible Human Carcinogen; NCI: Carcinogenesis Bioassay (feed); clear evidence: rat; no evidence: mouse. US EPA Gene-Tox Program, Negative: In vitro UDS— human fibroblast; TRP reversion; Negative: S. cerevisiae— homozygosis; Inconclusive: B. subtilis rec assay; E. coli polA without S9; Inconclusive: Histidine reversion—Ames test; Inconclusive: D. melanogaster sex-linked lethal Banned or Severely Restricted (many countries) (UN).[13] US EPA, FIFRA, 1998 Status of Pesticides: Supported. Very Toxic Substance (World Bank).[15] Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Clean Water Act: Section 311 Hazardous Substances/RQ 40CFR117.3 (same as CERCLA, see below); Section 313 Water Priority Chemicals (57FR41331, 9/9/92). US EPA Hazardous Waste Number (RCRA No.): P089. RCRA, 40CFR261, Appendix 8 Hazardous Constituents. RCRA 40CFR268.48; 61FR15654, Universal Treatment Standards: Wastewater (mg/L), 0.014; Nonwastewater (mg/kg), 4.6. RCRA 40CFR264, Appendix 9; TSD Facilities Ground Water Monitoring List. Suggested test method(s) (PQL μg/L): 8270 (10). Safe Drinking Water Act: Priority List (55 FR 1470) as parathion degradation. Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 100 lb (45.4 kg). Reportable Quantity (RQ): 10 lb (4.54 kg). EPCRA Section 313 Form R de minimis concentration reporting level: 1.0%. US DOT Regulated Marine Pollutant (49CFR172.101, Appendix B), severe pollutant. US DOT 49CFR172.101, Inhalation Hazard Chemical as organophosphates. Rotterdam Convention Annex III [Chemicals Subject to the Prior Informed Consent Procedure (PIC)] [parathion (all formulations—aerosols, dustable powder (DP), emulsifiable concentrate (EC), granules (GR), and wettable powders (WP)—of this substance are included, except capsule suspensions (CS))]. European/International Regulations: Hazard Symbol: T 1, N; Risk phrases: R24; R26/28; R48/25; R50/53; Safety phrases: S1/2; S28; S36/37; S45; S60; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): 3—Severe hazard to waters. Description: Parathion is a clear liquid when fresh; pale yellow to dark-brown liquid with a garlic-like odor. Commercial formulations use carrier solvents that may change the physical properties shown. Molecular weight 5 291.28; Specific gravity (H2O:1) 5 1.27; Boiling point 5 375 C; 157162 C at 6 mmHg (for CW agent); Freezing/Melting point 5 6.1 C; also listed at 2.9 C for
2058
Parathion
chemical warfare (CW) agent; Flash point 5 195 C (oc). Hazard Identification (based on NFPA-704 M Rating System): Health 4, Flammability 0, Reactivity 0. Slightly soluble in water; solubility 5 24 mg/L. Potential Exposure: A severely hazardous pesticide formulation. Those engaged in the manufacture, formulation, and application of this broad-spectrum insecticide. This material has also been used as a chemical warfare agent. Incompatibilities: Strong oxidizers may cause release of toxic phosphorus oxides. Organophosphates, in the presence of strong reducing agents such as hydrides, may form highly toxic and flammable phosphine gas. Keep away from alkaline materials. Attacks some plastics, rubbers, and coatings. Rapidly hydrolyzed by alkalis. Permissible Exposure Limits in Air OSHA PEL: 0.1 mg/m3 TWA [skin]. NIOSH REL: 0.05 mg/m3 TWA [skin]. ACGIH TLV®[1]: 0.05 mg/m3 TWA, inhalable fraction and vapor [skin]; not classifiable as a human carcinogen; BEI; 0.05 mg[creatinine]/g in urine, end-of-shift. NIOSH IDLH: 10 mg/m3. Protective Action Criteria (PAC)* TEEL-0: 0.1 mg/m3 PAC-1: 0.15 mg/m3 PAC-2: 1.5 mg/m3 PAC-3: 2 mg/m3 AEGLs (Acute Emergency Guideline Levels) & ERPGs (Emergency Response Planning Guideline) are in bold face. DFG MAK: 0.1 mg/m3 measured as the inhalable fraction TWA; Peak Limitation Category II(8) [skin]; Pregnancy Risk Group D; BAT: 100 μg[p-nitrophenol]/L in urine after several shifts (sampling time). Arab Republic of Egypt: TWA 0.1 mg/m3, [skin], 1993; Australia: TWA 0.1 mg/m3, [skin], 1993; Austria: MAK 0.1 mg/m3, [skin], 1999; Belgium: TWA 0.1 mg/m3, [skin], 1993; Denmark: TWA 0.1 mg/m3, [skin], 1999; Finland: TWA 0.1 mg/m3, short-term exposure limit 0.3 mg/m3, [skin], 1999; France: VME 0.1 mg/m3, [skin], 1999; the Netherlands: MAC-TGG 0.1 mg/m3, [skin], 2003; Japan: 0.1 mg/m3, [skin], 1999; Norway: TWA 0.05 mg/m3, 1999; the Philippines: TWA 0.1 mg/m3, [skin], 1993; Russia: STEL 0.05 mg/m3, 1993; Thailand: TWA 0.11 mg/m3, 1993; Turkey: TWA 0.1 mg/m3, [skin], 1993; United Kingdom: TWA 0.1 mg/m3, short-term exposure limit 0.3 mg/m3, [skin], 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: not classifiable as a human carcinogen. Several states have set guidelines or standards for parathion in ambient air[60] ranging from 0.238 μg/m3 (Kansas) to 0.33 μg/m3 (New York) to 0.5 μg/m3 (South Carolina) to 1.0 μg/m3 (North Dakota) to 1.6 μg/m3 (Virginia) to 1.87 μg/m3 (Pennsylvania) to 2.0 μg/m3 (Connecticut and Nevada). Determination in Air: Use NIOSH Analytical Method (IV) #5600, Organophosphorus pesticides; OSHA Analytical Method ID-62.
Permissible Concentration in Water: Russia set a MAC[35] of 3.0 μg/L in surface water and Mexico has set maximum permissible concentrations of 1.0 μg/L in coastal waters and 10.0 μg/L in estuaries. Several states have set guidelines for parathion in drinking water[61] ranging from 8.6 μg/L in Maine to 30.0 μg/L in California and Kansas. Determination in Water: Fish Tox 5 0.26514000 ppb MATC (EXTRA HIGH); Octanolwater coefficient: Log Kow 5 3.153.8. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Absorbed through the skin. Harmful Effects and Symptoms Short Term Exposure: Parathion irritates the eyes, skin, and respiratory tract. A cholinesterase inhibitor. Acute exposure to parathion may produce the following signs and symptoms: pinpoint pupils, blurred vision, headache, dizziness, muscle spasms, and profound weakness. Vomiting, diarrhea, abdominal pain, seizures, and coma may also occur. The heart rate may decrease following oral exposure or increase following dermal exposure. Hypotension (low blood pressure) is not uncommon. Respiratory symptoms include dyspnea (shortness of breath), respiratory depression, and respiratory paralysis. Psychosis may occur. This material is extremely toxic; the probable oral lethal dose is 550 mg/kg or between 7 drops and 1 teaspoonful for a 150-lb person. As little as 1 drop can endanger life if splashed in the eye. Toxicity is highest by inhalation. People at special risk are those with a history of glaucoma, cardiovascular disease, hepatic disease, renal disease, or central nervous system abnormalities. Some additional details on short-term exposure to parathion are as follows: Inhalation: Occasional human exposures at concentrations of 0.10.8 mg/m3 did not give rise to any symptoms. Occasional human exposure at 1.52.0 mg/m3 resulted in nausea and vomiting. Higher exposures can give rise to dizziness, blurred vision, wheezing, excessive salivation, and muscle and abdominal cramps. An estimated 1020 mg (1/1500 oz) may cause death. Skin: However, many human poisonings have occurred through extensive skin contact at unspecified levels. This is the greatest hazard for some workers. Symptoms of poisoning include nausea, vomiting, weakness, blurring of vision, and muscle cramps. NIOSH lists the following symptoms of exposure: irritation of the eyes, skin, respiratory system; miosis; rhinorrhea (discharge of thin nasal mucus); headache; chest tightness; wheezing, laryngeal spasm; salivation, cyanosis, anorexia, nausea, vomiting, abdominal cramps; diarrhea; sweating; muscle fasciculation; weakness, paralysis; giddiness, confusion, ataxia; convulsions, coma; low blood pressure; cardiac irregular/ irregularities. Long Term Exposure: Cholinesterase inhibitor; cumulative effect is possible. This chemical may damage the nervous system with repeated exposure, resulting in convulsions, respiratory failure. May cause liver damage. Human Tox 5 0.23100 ppb Health Advisory (EXTRA HIGH). Points of Attack: Respiratory system, central nervous system, cardiovascular system, eyes, skin, blood cholinesterase.
Parathion Medical Surveillance: NIOSH lists the following tests: blood serum; cholinesterase: whole blood (chemical/metabolite); cholinesterase: blood plasma; cholinesterase: blood plasma, red blood cells/count; urine (chemical/metabolite); urine (chemical/metabolite), end-of-shift; urine (chemical/ metabolite), end-of-workweek. NIOSH recommends that medical surveillance, including preemployment and periodic examinations, shall be made available to workers who may be occupationally exposed to parathion. Biologic monitoring is also recommended as an additional safety measure. Before employment and at regular times after that, the following are recommended: plasma and red blood cell cholinesterase levels (tests for the enzyme poisoned by this chemical). If exposure stops, plasma levels return to normal in 12 weeks while red blood cell levels may be reduced for 13 months. Do not drink any alcoholic beverages before or during use. Alcohol promotes absorption of organic phosphates. When cholinesterase enzyme levels are reduced by 25% or more below preemployment levels, risk of poisoning is increased, even if results are in lower ranges of “normal.” Reassignment to work not involving organophosphate or carbamate pesticides is recommended until enzyme levels recover. If symptoms develop or overexposure occurs, repeat the above tests as soon as possible and get an examination of the nervous system. Also, consider complete blood count. Consider chest X-ray following acute overexposure. Do not drink any alcoholic beverages before or during use. Alcohol promotes absorption of organic phosphates. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece
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respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: NIOSH: 0.5 mg/m3: CcrOv95 (APF 5 10) [any air-purifying half-mask respirator with organic vapor cartridge(s) in combination with an N95, R95, or P95 filter. The following filters may also be used: N99, R99, P99, N100, R100, P100] or Sa (APF 5 10) (any supplied-air respirator). 1.25 mg/m3: Sa:Cf (APF 5 25) (any supplied-air respirator operated in a continuous-flow mode) or PaprOvHie (APF 5 25) (any powered air-purifying respirator with an organic vapor cartridge in combination with a high-efficiency particulate filter). 2.5 mg/m3: CcrFOv100 (APF 5 50) [any air-purifying full-face-piece respirator equipped with organic vapor cartridge(s) in combination with an N100, R100, or P100 filter] or SaT: Cf (APF 5 50) (any supplied-air respirator that has a tight-fitting face-piece and is operated in a continuous-flow mode) or PaprTOvHie (APF 5 50) [any powered, air-purifying respirator with a tight-fitting face-piece and organic vapor cartridge(s) in combination with a high-efficiency particulate filter] or SCBAF (APF 5 50) (any self-contained breathing apparatus with full face-piece) or SaF (APF 5 50) (any supplied-air respirator with a full face-piece). 10 mg/m3: Sa: Pd,Pp (APF 5 1000) (any supplied-air respirator operated in a pressure-demand or other positive-pressure mode). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd,Pp (APF 5 10,000) (any self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positivepressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: GmFOv100 (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or back-mounted organic vapor canister having an N100, R100, or P100 filter] or SCBAE (any appropriate escape-type, self-contained breathing apparatus). Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store where possible leakage from containers will not endanger the worker. Maintain regular inspection of containers for leakage. Store in tightly closed containers in a cool, well-ventilated area away from oxidizers and alkaline material. Where possible, automatically pump liquid from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of 5 gallons or more of this chemical should be grounded and bonded. Drums must be equipped with self-closing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing
2060
Paris green
containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: Organophosphorus pesticides, liquid, toxic, require a shipping label of “POISONOUS/TOXIC MATERIALS.” Parathion falls in DOT Hazard Class 6.1 and Packing Group I. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Ventilate area of spill or leak. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is not very combustible. Poisonous gases, including carbon monoxide, sulfur oxides, phosphorous oxides, nitrogen oxides, are produced in fire. Use dry chemical, carbon dioxide, or alcohol foam extinguishers. Vapors are heavier than air and will collect in low areas. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant ($100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. In accordance with 40CFR165, follow recommendations for the disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by contacting your local or federal environmental control agency or by contacting your regional EPA office. One manufacturer recommends the use of a detergent in a 5% trisodium phosphate solution for parathion disposal and
cleanup problems. For parathion disposal in general, however, the recommended method is incineration (816 C, 0.5 s minimum for primary combustion; 1204 C, 1.0 s for secondary combustion) with adequate scrubbing and ash disposal facilities.[22] References National Institute for Occupational Safety and Health. (1976). Criteria for a Recommended Standard: Occupational Exposure to Parathion, NIOSH Document No. 76-190 Sax, N. I. (Ed.). (1983). Dangerous Properties of Industrial Materials Report, 3, No. 3, 9297 US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Parathion. Washington, DC: Chemical Emergency Preparedness Program New York State Department of Health. (March 1986). Chemical Fact Sheet: Parathion (Version 2 and Version 3). Albany, NY: Bureau of Toxic Substance Assessment US Environmental Protection Agency, Special Review and Reregistration Division Office of Pesticide Programs. (1998). Agency Status of Pesticides in Registration, Reregistration, and Special Review (Rainbow Report). Washington, DC
Paris green
P:0180
Molecular Formula: C4H6As6Cu4O16 Synonyms: Acetoarsenite de cuivre (French); Acetoarsenito de cobre (Spanish); Basle green; C.I. 77410; C.I. Pigment green 21; Copper acetoarsenite; Cupric acetoarsenite; Emerald green; ENT884; French green; Imperial green; King’s green; Meadow green; Mineral green; Mitis green; Moss green; Mountain green; Neuwied green; New green; Paris green; Parrot green; Patent green; O-P-G bait; Powder green; Schweinfurtergruen (German); Schweinfurt green; Sowbug & cutworm bait; Swedish green; Vienna green CAS Registry Number: 12002-03-8 RTECS® Number: GL6475000 UN/NA & ERG Number: UN1585/151 Regulatory Authority and Advisory Bodies Clean Air Act: Hazardous Air Pollutants (Title I, Part A, Section 112); List of high-risk pollutants (Section 63.74) as arsenic compounds. Clean Water Act: Section 311 Hazardous Substances/RQ 1 lb (0.454 kg); Toxic Pollutant (Section 401.15) as copper and compounds; Section 313 Water Priority Chemicals (57FR41331, 9/9/92). Safe Drinking Water Act 47FR9352 Regulated chemical: MCL, 0.05 mg/L (Section 141.11) applies only to community water systems (arsenic). RCRA 40CFR264, Appendix 9; TSD Facilities Ground Water Monitoring List. Suggested test method(s) (PQL μg/L): 6010 (60); 7210 (200) Note: All species in the ground water that contain copper are included.
Paris green Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 500/10,000 lb (227/4540 kg). Reportable Quantity (RQ): 500 lb (227 kg). EPCRA Section 313 Form R de minimis concentration reporting level: 1.0%. US DOT Regulated Marine Pollutant (49CFR172.101, Appendix B) as arsenates, liquid, n.o.s.; arsenates, solid, n.o.s.; arsenical pesticides liquid, toxic, flammable, n.o.s. California Proposition 65 Chemical: Cancer 2/27/87. Canada: Priority Substance List & Restricted Substances/ Ocean Dumping FORBIDDEN (CEPA), National Pollutant Release Inventory (NPRI) (arsenic compounds). Canada, WHMIS, Ingredients Disclosure List Concentration 1.0% arsenic, water-soluble compounds. European/International Regulations: Hazard Symbol: T, N; Risk phrases: R45; R23/25; R50/53; Safety phrases: S53; S45; S60; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): 3—Severe hazard to waters. Description: Paris green (copper acetoarsenite) is an odorless emerald green crystalline powder which decomposes upon heating. Molecular weight 5 1013.78. Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 1, Reactivity 0. Insoluble in water. Potential Exposure: This material is used primarily as an insecticide; it may be used as a wood preservative and a pigment, particularly for ships and submarines; and also finds use as an anthelmintic. Incompatibilities: Can react vigorously with oxidizers. Emits highly toxic arsenic fumes on contact with acid or acid fumes; and in elevated temperatures. Permissible Exposure Limits in Air Arsenic, organic compounds OSHA PEL: 0.5 mg[As]/m3 TWA. NIOSH REL: Not established. See NIOSH Pocket Guide, Appendix A. ACGIH TLV®[1]: 0.01 mg[As]/m3 TWA; Confirmed Human Carcinogen; BEI established. Protective Action Criteria (PAC) Paris green; cupric acetoarsenite TEEL-0: 1.13 mg/m3 PAC-1: 3.38 mg/m3 PAC-2: 22 mg/m3 PAC-3: 22 mg/m3 As arsenic, organic compounds TEEL-0: 0.5 mg/m3 PAC-1: 1.5 mg/m3 PAC-2: 2.5 mg/m3 PAC-3: 350 mg/m3 Arab Republic of Egypt: TWA 0.2 mg/m3, 1993; Australia: TWA 0.05 mg/m3, carcinogen, 1993; Belgium: TWA 0.2 mg/m3, 1993; Denmark: TWA 0.05 mg/m3, 1999; Finland: carcinogen, 1993; France: VME 0.2 mg/m3, 1993; Hungary: STEL 0.5 mg/m3, carcinogen, 1993; India: TWA 0.2 mg/m3, 1993; Norway: TWA 0.02 mg/m3, 1999; the Philippines: TWA 0.5 mg/m3, 1993; Poland: MAC (TWA)
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0.01 mg/m3, 1999; Sweden: NGV 0.03 mg/m3, carcinogen, 1999; Switzerland: TWA 0.1 mg/m3, carcinogen, 1999; Thailand: TWA 0.5 mg/m3, 1993; Turkey: TWA 0.5 mg (As)/m3; TWA 0.5 mg/m3, 1993; United Kingdom: TWA 0.1 mg/m3, carcinogen, 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH: TLV: Confirmed Human Carcinogen. Russia[43] set a MAC of 0.003 mg/m3 on a daily average basis for residential areas. Several states have set guidelines or standards for arsenic in ambient air[60]: 0.06 mg/m3 (California Prop. 65), 0.0002 μg/m3 (Rhode Island), 0.00023 μg/m3 (North Carolina), 0.024 μg/m3 3 (Pennsylvania), 0.05 μg/m (Connecticut), 0.070.39 μg/m3 (Montana), 0.67 μg/m3 (New York), 1.0 μg/m3 (South Carolina), 2.0 μg/m3 (North Dakota), 3.3 μg/m3 (Virginia), 5 μg/m3 (Nevada). Determination in Air: NIOSH Analytical Methods (inorganic arsenic): #7300, #7301, #7303, #7900, #9102; OSHA Analytical Methods ID-105. The American Conference of Government Industrial Hygienists (ACGIH) Method 803 measures total particulate arsenic in air. Permissible Concentration in Water: EPA[6] recommends a zero concentration of arsenic for human health reasons but has set a guideline of 50 μg/L[61] for drinking water. Determination in Water: For arsenic: The atomic absorption graphite furnace technique is often used for measurement of total arsenic in water. It has also been standardized by EPA. Total arsenic may be determined by digestion followed by silver diethyldithiocarbamate; an alternative is atomic absorption; another is inductively coupled plasma (ICP) optical emission spectrometry. See OSHA Analytical Method #ID-105 for arsenic. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: It may cause eye and respiratory tract irritation. Industrial exposure may cause dermatitis. This material is extremely toxic; the probable oral lethal dose for humans is 550 mg/kg or between 7 drops and 1 teaspoonful for a 150-lb person. Some absorption may occur through the skin and by inhalation, but most poisonings result from ingestion. Symptoms usually appear 1/2 to 1 h after ingestion, but may be delayed. Causes gastric disturbance, tremors, muscular cramps, and nervous collapse, which may lead to death. Symptoms of exposure also include a sweetish, metallic taste and garlicky odor; difficulty in swallowing; abdominal pain; vomiting and diarrhea; dehydration; rapid heartbeat; dizziness and headache; and eventually coma; sometimes convulsions; and death. Long Term Exposure: May cause liver damage. Arsenic compounds may cause blood, kidneys, and nervous system damage, and skin abnormalities may develop. See also entries for “Arsenic” and “Copper.” Points of Attack: Liver, kidneys, blood, skin. Medical Surveillance: Liver and kidney function tests. Blood tests including CBC.
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Paris green
First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Note to physician: For severe poisoning BAL [British AntiLewisite, dimercaprol, dithiopropanol (C3H8OS2)] has been used to treat toxic symptoms of certain heavy metal poisoning—including arsenic. Although BAL is reported to have a large margin of safety, caution must be exercised, because toxic effects may be caused by excessive dosage. Most can be prevented by premedication with 1-ephedrine sulfate (CAS: 134-72-5). For milder poisoning penicillamine (not penicillin) has been used, both with mixed success. Side effects occur with such treatment and it is never a substitute for controlling exposure. It can only be done under strict medical care. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Specific engineering controls are required under OSHA 1910.1018, Inorganic Arsenic. See also NIOSH Criteria Document #75149, “Inorganic Arsenic.” Respirator Selection: Copper dusts and mists: 5 mg/m3: Qm (APF 5 25) (any quarter-mask respirator). 10 mg/m3: Any particulate respirator equipped with an N95, R95, or P95 filter (including N95, R95, and P95 filtering facepieces) except quarter-mask respirators. The following filters may also be used: N99, R99, P99, N100, R100, P100; or Sa (APF 5 10) (any supplied-air respirator). 25 mg/m3: Sa:Cf (APF 5 25) (any supplied-air respirator operated in a continuous-flow mode); PaprHie (APF 5 25) (any powered, air-purifying respirator with a high-efficiency particulate filter). 50 mg/m3: 100F (APF 5 50) (any air-purifying, fullface-piece respirator with an N100, R100, or P100 filter) or PaprTHie (APF 5 50) (any powered, air-purifying respirator with a tight-fitting face-piece and a high-efficiency particulate filter) or SCBAF (APF 5 50) (any self-contained breathing apparatus with a full face-piece) or SaF
(APF 5 50) (any supplied-air respirator with a full facepiece). 100 mg/m3: SaF: Pd,Pp (APF 5 2000) (any suppliedair respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd,Pp (APF 5 10,000) (any self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positivepressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: 100F (APF 5 50) (any airpurifying, full-face-piece respirator with an N100, R100, or P100 filter) or SCBAE (any appropriate escape-type, selfcontained breathing apparatus). Note: Substance reported to cause eye irritation or damage; may require eye protection. Arsenic: At concentrations above the NIOSH REL, or where there is no REL, at any detectable concentration: Sa (APF 5 10) (any supplied-air respirator) or SCBAF (APF 5 50) (any self-contained breathing apparatus with a full face-piece). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd,Pp (APF 5 10,000) (any self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary, self-contained breathing apparatus operated in a pressuredemand or other positive-pressure mode). Escape: GmFAg100 (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or backmounted acid gas canister having an N100, R100, or P100 filter] or SCBAE (any appropriate escape-type, selfcontained breathing apparatus). Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with copper acetoarsenite you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, well-ventilated area, away from strong bases, strong acids, and moisture. Where possible, automatically pump liquid from drums or other storage containers to process containers. Shipping: Copper acetoarsenite requires a shipping label of “POISONOUS/TOXIC MATERIALS.” Copper acetoarsenite falls in Hazard Class 6.1 and Packing Group II. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Stay upwind; keep out of low areas. Do not touch spilled material. Take up small spills with sand or other noncombustible absorbent material and place in sealed containers for later disposal. For small dry spills, use a clean shovel to place material in clean, dry
Pentaborane container. For large spills, dike far ahead of spill for later disposal. Use water spray to knock down dust. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical may burn but does not easily ignite. Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Poisonous fumes are produced in fire, including arsenic oxide and copper. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant ($100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. In accordance with 40CFR165, follow recommendations for the disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by contacting your local or federal environmental control agency or by contacting your regional EPA office. References New Jersey Department of Health and Senior Services. (January 1999). Hazardous Substances Fact Sheet: Copper Acetoarsenite. Trenton, NJ US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Paris Green. Washington, DC: Chemical Emergency Preparedness Program
Pentaborane
P:0190
Molecular Formula: B5H9 Synonyms: Dihydropentaborane (9); Pentaborane (9); Pentaborane undecahydride; Pentaborano (Spanish); (9)Pentaboron nonahydride; Pentaboron nonahydride; Pentaboron undecahydride; Stable pentaborane CAS Registry Number: 19624-22-7 RTECS® Number: RY8925000
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UN/NA & ERG Number: UN1380/135 EC Number: 243-194-4 Regulatory Authority and Advisory Bodies Very Toxic Substance (World Bank).[15] Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Reportable Quantity (RQ): 500 lb (227 kg). Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 500 lb (227 kg). US DOT 49CFR172.101, Inhalation Hazardous Chemical. Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: not listed in Annex 1. WGK (German Aquatic Hazard Class): No value assigned. Description: Pentaborane is a colorless, volatile liquid with an unpleasant, sweetish odor, like sour milk. The odor threshold is 0.8 ppm. Molecular weight 5 63.14; Specific gravity (H2O:1) 5 0.62; Boiling point 5 60 C; Freezing/ Melting point 5 47 C; Vapor pressure 5 171 mmHg at 25 C; Flash point 5 30 C; Autoignition temperature: about 35 C. Explosive limits: LEL 5 0.42%; UEL 5 98%. Hazard Identification (based on NFPA-704 M Rating System): Health 4, Flammability 4, Reactivity 2. Reacts with water. Potential Exposure: Pentaborane is used in rocket propellants and in gasoline additives. Incompatibilities: Reacts on contact with oxidizers, halogens, water, halogenated hydrocarbons. May ignite spontaneously in moist air, decomposes at 150 C. Corrosive to natural rubber. Hydrolyzes slowly with heat in water to form boric acid. Contact with solvents, such as ketones, ethers, esters, forms shock-sensitive compounds. Corrosive to natural rubber and some synthetic rubber; some lubricants. Permissible Exposure Limits in Air Conversion factor: 1 ppm 5 2.58 mg/m3 at 25 C & 1 atm. OSHA PEL: 0.005 ppm/0.01 mg/m3 TWA. NIOSH REL: 0.005 ppm/0.01 mg/m3 TWA; 0.015 ppm/ 0.03 mg/m3 STEL. 0.005 ppm/0.013 mg/m3 TWA; ACGIH TLV®[1]: 3 0.015 ppm/0.039 mg/m STEL. NIOSH IDLH: 1 ppm. Protective Action Criteria (PAC)* TEEL-0: 0.005 mg/m3 PAC-1: 0.015 mg/m3 PAC-2: 0.14 mg/m3 PAC-3: 0.70 mg/m3 *AEGLs (Acute Emergency Guideline Levels) & ERPGs (Emergency Response Planning Guideline) are in bold face. DFG MAK: 0.005 ppm/0.013 mg/m3 TWA; Peak Limitation Category II(2). Arab Republic of Egypt: TWA 0.1 mg/m3, [skin], 1993; Australia: TWA 0.1 mg/m3, [skin], 1993; Austria: MAK 0.1 mg/m3, [skin], 1999; Belgium: TWA 0.1 mg/m3, [skin], 1993; Denmark: TWA 0.1 mg/m3, [skin], 1999; Finland: TWA 0.1 mg/m3, short-term exposure limit 0.3 mg/m3,
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Pentaborane
[skin], 1999; France: VME 0.1 mg/m3, [skin], 1999; the Netherlands: MAC-TGG 0.1 mg/m3, [skin], 2003; Japan: 0.1 mg/m3, [skin], 1999; Norway: TWA 0.05 mg/m3, 1999; the Philippines: TWA 0.1 mg/m3, [skin], 1993; Russia: STEL 0.05 mg/m3, 1993; Thailand: TWA 0.11 mg/m3, 1993; Turkey: TWA 0.1 mg/m3, [skin], 1993; United Kingdom: TWA 0.1 mg/m3, short-term exposure limit 0.3 mg/m3, [skin], 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: not classifiable as a human carcinogen. Several states have set guidelines or standards for pentaborane in ambient air[60] ranging from 0.16 μg/m3 (Virginia) to 0.2 μg/m3 (Connecticut) to 1.03.0 μg/m3 (North Dakota) to 2.0 μg/m3 (Nevada). Determination in Air: No Analytical Method available. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Causes severe irritation to the respiratory tract. Pentaborane may affect the central nervous system, resulting in visual disturbances, poor judgment, behavioral changes, loss of recent memory, nausea, vomiting, drowsiness, and difficulty in focusing. Inhalation of higher concentrations may cause headache, dizziness, nervous excitation, muscular pain, muscle incoordination, cramps, tremors, convulsions, and coma. Death can occur by central nervous system poisoning. Points of Attack: Central nervous system, eyes, skin. Medical Surveillance: Preemployment and periodic physical examinations to determine the status of the workers’ general health should be performed. These examinations should be concerned especially with any history of central nervous system disease, personality or behavioral changes, as well as liver, kidney, or pulmonary disease of any significant nature. Chest X-ray, blood, liver, and renal function studies may be helpful. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be
worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: 0.05 ppm: Sa (APF 5 10) (any supplied-air respirator). 0.125 ppm: Sa:Cf (APF 5 25) (any supplied-air respirator operated in a continuous-flow mode). 0.25 ppm: SaT: Cf (APF 5 50) (any supplied-air respirator that has a tight-fitting face-piece and is operated in a continuous-flow mode) or SCBAF (APF 5 50) (any self-contained breathing apparatus with a full face-piece) or SaF (APF 5 50) (any supplied-air respirator with a full facepiece). 1 ppm: Sa: Pd,Pp (APF 5 1000) (any supplied-air respirator operated in a pressure-demand or other positivepressure mode). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd,Pp (APF 5 10,000) (any self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: GmFS (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or back-mounted canister providing protection against the compound of concern] or SCBAE (any appropriate escape-type, self-contained breathing apparatus). Note: Make certain respirator has no exposed rubber gaskets. Storage: Color Code—Red: Flammability Hazard: Store in a flammable materials storage area. Prior to working with this chemical you should be trained on its proper handling and storage. Before entering confined space where this chemical may be present, check to make sure that an explosive concentration is not a danger. Store in tightly closed containers in a cool, well-ventilated area away from oxidizers, halogens, water, halogenated hydrocarbons. Where possible, automatically pump liquid from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of 5 gallons or more of this chemical should be grounded and bonded. Drums must be equipped with self-closing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: This compound requires a shipping label of “SPONTANEOUSLY COMBUSTIBLE, POISONOUS/ TOXIC MATERIALS.” It falls in Hazard Class 4.2 and Packing Group I. A plus sign (1) indicates that the
Pentachlorobenzene designated proper shipping name and hazard class of the material must always be shown whether or not the material or its mixtures or solutions meet the definitions of the class. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Establish forced ventilation to keep levels below explosive limit. Do not touch spilled material, stop leak if you can do it without risk. For spills, dike for later disposal and do not apply water unless directed to do so. Clean up only under supervision of an expert. Keep unnecessary people away; isolate hazard area and deny entry. Stay upwind; keep out of low areas. Ventilate closed spaces before entering them. Avoid breathing vapors, and keep upwind. Avoid bodily contact with the material. Do not handle broken packages without protective equipment. Wash away any material which may have contacted the body with copious amounts of water or soap and water. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Initial isolation and protective action distances Distances shown are likely to be affected during the first 30 min after materials are spilled and could increase with time. If more than one tank car, cargo tank, portable tank, or large cylinder involved in the incident is leaking, the protective action distance may need to be increased. You may need to seek emergency information from CHEMTREC at (800) 424-9300 or seek professional environmental engineering assistance from the US EPA Environmental Response Team at (908) 548-8730 (24-h response line). Small spills (From a small package or a small leak from a large package) First: Isolate in all directions (feet/meters) 200/60 Then: Protect persons downwind (miles/kilometers) Day 0.4/0.6 Night 1.4/2.3 Large spills (From a large package or from many small packages) First: Isolate in all directions (feet/meters) 1250/400 Then: Protect persons downwind (miles/kilometers) Day 2.9/4.7 Night 5.5/8.9 Fire Extinguishing: This chemical is a combustible liquid. Poisonous gases, including boron, are produced in fire. Ignites spontaneously in air. Reacts violently with halogenated extinguishing agents. Fires tend to reignite. If material is on fire or involved in fire, do not extinguish unless flow can be stopped. Do not use water. Extinguish small fires with
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dry chemical or carbon dioxide. For large fires withdraw and let burn. Move container from fire area if you can do it without risk. Cool containers that are exposed to flames with water from the side until well after fire is out. For massive fire in cargo area, use unmanned hose holder or monitor nozzles; if this is impossible, withdraw from area and let fire burn. Wear positive pressure breathing apparatus and full protective clothing. If fire becomes uncontrollable or container is exposed to direct flame—evacuate for a radius of 1500 feet. If material is leaking (not on fire), downwind evacuation must be considered. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Incineration with aqueous scrubbing of exhaust gases to remove B2O3 particulates. Reference US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Pentaborane. Washington, DC: Chemical Emergency Preparedness Program
Pentachlorobenzene
P:0200
Molecular Formula: C6HCl5 Synonyms: Benzene, pentachloro-; 1,2,3,4,5-Pentachlorobenzene; QCB CAS Registry Number: 608-93-5 RTECS® Number: DA6640000 UN/NA & ERG Number: UN3077/171 EC Number: 210-172-0 [Annex I Index No.: 602-074-00-5] Regulatory Authority and Advisory Bodies Carcinogenicity: EPA: Not Classifiable as to human carcinogenicity. TSCA: Subject to a proposed or final SNUR; Subject to a Section 4 test rule. US EPA Hazardous Waste Number (RCRA No.): U183. RCRA, 40CFR261, Appendix 8 Hazardous Constituents. RCRA 40CFR268.48; 61FR15654, Universal Treatment Standards: Wastewater (mg/L), 0.055; Nonwastewater (mg/kg), 10.
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Pentachlorobenzene
RCRA 40CFR264, Appendix 9; TSD Facilities Ground Water Monitoring List. Suggested test method(s) (PQL μg/L): 8270 (10). Reportable Quantity (RQ): 10 lb (4.54 kg). List of Stockholm Convention POPs: Annex A (Elimination); Annex C (Unintentional production and release). European/International Regulations: Hazard Symbol: Risk phrases: F, Xn, N; R11; R22; R50/53; Safety phrases: S2; S41; S46; S50; S60; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): 3—Severe hazard to waters. Description: Pentachlorobenzene is a colorless crystalline solid with a pleasant aroma. Molecular weight 5 250.32; Boiling point 5 277 C; Freezing/Melting point 5 86 C. Insoluble in water; solubility 0.65 mg/L. Potential Exposure: Pentachlorobenzene is used primarily as a precursor in the synthesis of the fungicide pentachloronitrobenzene, and as a flame retardant. Drug/Therapeutic Agent; Fungicide; bactericide; wood preservative; industrial insecticides; organochlorine; Reproductive Effect; Tumor data. Incompatibilities: Polychlorinated hydrocarbons can react with oxidizers and may react violently with aluminum, liquid oxygen, potassium, sodium. Permissible Exposure Limits in Air Protective Action Criteria (PAC) TEEL-0: 0.04 mg/m3 PAC-1: 0.125 mg/m3 PAC-2: 0.75 mg/m3 PAC-3: 400 mg/m3 Determination in Air: Filter/XAD-2; workup with hexane; GC/ECD; NIOSH Analytical Method (IV) #5517, Polychlorobenzenes. Determination in Water: A persistent organic pollutant. Log Kow 5 4.755.75. Permissible Concentration in Water: The US EPA has set a criterion of 0.5 μg/L based on toxicity studies. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: May affect the nervous system. LD505 (oral-rat) 1080 mg/kg. Long Term Exposure: Pentachlorobenzene may affect the liver and kidneys, causing tissue lesions. Limited animal studies have produced developmental effects and decreased body weights in fetuses. Points of Attack: Liver, kidneys. Medical Surveillance: Liver and kidney function tests. First Aid: Skin Contact[52]: Flood all areas of body that have contacted the substance with water. Do not wait to remove contaminated clothing; do it under the water stream. Use soap to help assure removal. Isolate contaminated clothing when removed to prevent contact by others. Eye Contact: Remove any contact lenses at once. Flush eyes well with copious quantities of water or normal saline for at
least 2030 min. Seek medical attention. Inhalation: Leave contaminated area immediately; breathe fresh air. Proper respiratory protection must be supplied to any rescuers. If coughing, difficult breathing, or any other symptoms develop, seek medical attention at once, even if symptoms develop many hours after exposure. Ingestion: If convulsions are not present, give a glass or two of water or milk to dilute the substance. Assure that the person’s airway is unobstructed and contact a hospital or poison center immediately for advice on whether or not to induce vomiting. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in pressure-demand or other positive-pressure mode. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in a refrigerator or a cool, dry place. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: The name of this material is not in the DOT list of materials[19] for label and packaging standards. However, based on regulations, it may be classified[52] as an Environmentally hazardous substances, solid, n.o.s. This chemical requires a shipping label of “CLASS 9.” It falls in Hazard Class 9 and Packing Group III.[20, 21] Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources.[52] Dampen spilled material with alcohol to avoid dust, then transfer material to a suitable container. Use absorbent dampened with alcohol to pick up remaining material. Wash surfaces well with soap and water. Seal all wastes in vapor-tight plastic bags for eventual disposal. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters
Pentachloroethane waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible solid. Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Poisonous gases are produced in fire, including chlorine. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant ($100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. Incineration after mixing with another combustible fuel. Care must be exercised to assure complete combustion to prevent the formation of phosgene. An acid scrubber is necessary to remove the halo acids produced. References US Environmental Protection Agency. (April 30, 1980). Pentachlorobenzene, Health and Environmental Effects Profile No. 141. Washington, DC: Office of Solid Waste US EPA. (1980). Chlorinated Benzenes: Ambient Water Quality Criteria. Washington, DC Sax, N. I. (Ed.). (1986). Dangerous Properties of Industrial Materials Report, 6, No. 1, 105107
Pentachloroethane
P:0210
Molecular Formula: C2HCl5 Common Formula: CCl3CHCl2 Synonyms: Ethane pentachloride; Ethane, pentachloro-; NCI-C53894; Pentachloraethan (German); Pentachlorethane (French); Pentacloroetano (Spanish); Pentalin CAS Registry Number: 76-01-7 RTECS® Number: KI6300000 UN/NA & ERG Number: UN1669/151 EC Number: 200-925-1 [Annex I Index No.: 602-017-00-4] Regulatory Authority and Advisory Bodies Carcinogenicity: NCI: Carcinogenesis Studies (gavage); clear evidence: mouse; equivocal evidence: rat; IARC: Animal Limited Evidence; Human No Adequate Data, not classifiable as carcinogenic to humans, Group 3, 1999.
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Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. US EPA Hazardous Waste Number (RCRA No.): U184. RCRA, 40CFR261, Appendix 8 Hazardous Constituents. RCRA 40CFR268.48; 61FR15654, Universal Treatment Standards: Wastewater (mg/L), 0.055; Nonwastewater (mg/ kg), 6.0. RCRA 40CFR264, Appendix 9; TSD Facilities Ground Water Monitoring List. Suggested test method(s) (PQL μg/ L): 8240 (5); 8270 (10). Reportable Quantity (RQ): 10 lb (4.54 kg). EPCRA Section 313 Form R de minimis concentration reporting level: 1.0%. US DOT Regulated Marine Pollutant (49CFR172.101, Appendix B). Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: Hazard Symbol: T, N; Risk phrases: R40; R48/23; R51/53; Safety phrases: S1/2; S23; S36/37; S45; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): No value assigned. Description: Pentachloroethane is a colorless, heavy, nonflammable liquid with a sweetish chloroform- or camphorlike odor. Molecular weight 5 202.28; Boiling point 5 162 C; Freezing/Melting point 5 29 C; Flash point 5 75 C (cc). Hazard Identification (based on NFPA704 M Rating System): Health 3, Flammability 2, Reactivity 0. Practically insoluble in water. Potential Exposure: Compound Description: Tumorigen, Drug, Mutagen. Pentachloroethane is used in the manufacture of tetrachloroethylene and as a solvent for cellulose acetate, certain cellulose ethers, resins, and gums. It is also used as a drying agent for timber by immersion at temperatures greater than 100 C. Incompatibilities: May self-ignite. Violent reaction with alkali metals (i.e., lithium, sodium, potassium, rubidium, cesium, francium) will produce spontaneous explosive chloroacetylenes. Shock- and friction-sensitive material formed by mixture with potassium. Permissible Exposure Limits in Air NIOSH REL: Handle with caution; See NIOSH Pocket Guide, Appendix C. Protective Action Criteria (PAC) TEEL-0: 46 mg/m3 PAC-1: 126 mg/m3 PAC-2: 500 mg/m3 PAC-3: 500 mg/m3 DFG MAK: 5 ppm/42 mg/m3 TWA; Peak Limitation Category II(2). Rumania: TWA 30 mg/m3; Yugoslavia: MAC 5 ppm/ 40 mg/m3. Determination in Air: Use NIOSH Analytical Method (IV) #2517. Permissible Concentration in Water: To protect freshwater aquatic life: 7240 μg/L on an acute toxicity basis and 1100 μg/L on a chronic basis. To protect saltwater aquatic
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Pentachloroethane
life: 390 μg/L on an acute toxicity basis and 231 μg/L on a chronic basis. To protect human health—no criteria derived due to insufficient data.[6] Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Pentachloroethane is an irritant and a strong central nervous system depressant. Pentachloroethane has a strong narcotic effect. Symptoms include prompt nausea, vomiting, abdominal pain with diarrhea, headaches, dizziness, confusion, drowsiness, and occasionally, convulsions. Visual disturbances may arise followed by coma and possible death from respiratory arrest or circulatory collapse. Death may occur by respiratory arrest or circulatory collapse. Occasionally, sudden death may occur due to ventricular fibrillation. Other effects may include weight gain, edema, loss of appetite, jaundice, and pain (due to enlarged liver). The chemical is very toxic with a probable oral lethal dose of 50500 mg/kg or between 1 teaspoon and 1 oz for a 150-lb person. In animals: irritation of eyes, skin; weakness, restlessness, irregular/irregularities of respiration, muscle incoordination; liver, kidney, lung changes (NIOSH). Long Term Exposure: Exposure to this material may result in injury to the liver, lungs, and kidneys. Points of Attack: Eyes, skin, respiratory system, central nervous system, liver, kidneys. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Keep victim quiet and maintain normal body temperature. Effects may be delayed; keep victim under observation. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a
NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in pressure-demand or other positive-pressure mode. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in a refrigerator away from alkalis, reactive metals, water. Where possible, automatically pump liquid from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of 5 gallons or more of this chemical should be grounded and bonded. Drums must be equipped with self-closing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. A regulated, marked area should be established where this chemical is handled, used, or stored in compliance with OSHA Standard 1910.1045. Shipping: This compound requires a shipping label of “POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 6.1 and Packing Group II. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Ventilate area of spill or leak. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible liquid. Poisonous gases, including chlorine, are produced in fire. Fires should be extinguished using water, carbon dioxide, or dry chemical. Move container from fire area if you can do so without risk. Fight fire from maximum distance. Dike fire control water for later disposal; do not scatter the material. Keep unnecessary people away; isolate hazard area and deny entry. Stay upwind; keep out of low areas. Ventilate closed spaces before entering them. Wear positive pressure breathing apparatus and special protective clothing. Remove and isolate contaminated clothing at the site.
Pentachloronaphthalene Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant ($100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. Incineration after mixing with another combustible fuel. Care must be exercised to assure complete combustion to prevent the formation of phosgene. An acid scrubber is necessary to remove the halo acids produced.[22] References National Institute for Occupational Safety and Health. (1977). Profiles on Occupational Hazards for Criteria Document Priorities: Pentachloroethane, Report PB274,073. Cincinnati, OH, pp. 303305 US Environmental Protection Agency. (1980). Chlorinated Ethanes: Ambient Water Quality Criteria. Washington, DC US Environmental Protection Agency. (January 4, 1983). Chemical Hazard Information Profile Draft Reports: Pentachloroethane. Washington, DC US Environmental Protection Agency. (October 31, 1985). Chemical Hazard Information Profile: Pentachloroethane. Washington, DC: Chemical Emergency Preparedness Program
Pentachloronaphthalene
P:0220
Molecular Formula: C10H3Cl5 Synonyms: Halowax 1013; Naphthalene, pentachloro-; 1,2,3,4,5-Pentachloronaphthalene CAS Registry Number: 1321-64-8 RTECS® Number: QK0300000 EC Number: 215-320-8 [Annex I Index No.: 602-041-00-5] Regulatory Authority and Advisory Bodies US EPA GENETOX PROGRAM: Positive: Histidine reversion—Ames test, 1988. Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section.
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Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: Hazard Symbol: Xn, N; Risk phrases: R21/22; R36/38; R50/53; Safety phrases: S2 (see Appendix 4). WGK (German Aquatic Hazard Class): 3—Severe hazard to waters. Description: Pentachloronaphthalene is a pale yellow or white solid powder with an aromatic odor. Molecular weight 5 300.38; Specific gravity (H2O:1) 5 1.67; Boiling point 5 335.6 C. Freezing/Freezing/Melting point 5 120 C; Vapor pressure 5 ,1 mmHg at 25 C. Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 0, Reactivity 0. Insoluble in water. Potential Exposure: Compound Description: Tumorigen, Mutagen. Used in electric wire insulation, in additives to specialized lubricants, and as a fire- and water-proofing agent. Incompatibilities: Violent reaction with strong oxidizers, aluminum, liquid oxygen, potassium, sodium. Heat may contribute to instability. Permissible Exposure Limits in Air OSHA PEL: 0.5 mg/m3 TWA [skin]. NIOSH REL: 0.5 mg/m3 TWA [skin]. ACGIH TLV®[1]: 0.5 mg/m3 TWA [skin]. No TEEL available. DFG MAK: 0.5 mg/m3 TWA [skin]. Australia: TWA 0.5 mg/m3, 1993; Austria: MAK 0.5 mg/m3, [skin], 1999; Belgium: TWA 0.5 mg/m3, 1993; Denmark: TWA 0.5 mg/m3, [skin], 1999; France: VME 0.5 mg/m3, 1999; Norway: TWA 0.5 mg/m3, 1999; the Netherlands: MAC-TGG 0.5 mg/m3, 2003; Poland: MAC (TWA) 0.5 mg/m3, MAC (STEL) 1.5 mg/m3, 1999; Sweden: NGV 0.2 mg/m3, KTV 0.3 mg/m3, [skin], 1999; Switzerland: MAK-W 0.5 mg/m3, KZG-W 2.5 mg/m3, [skin], 1999; Turkey: TWA 0.5 mg/m3, [skin], 1993; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: TWA 0.5 mg/m3 [skin]. When skin contact also occurs, you may be overexposed, even though air levels are less than the limit listed above. Determination in Air: Use NIOSH II(2), Method #S9. Determination in Water: Octanolwater coefficient: Log Kow 5 8.739.13 (ICSC). Routes of Entry: Inhalation, skin absorption, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Irritates the eyes, skin, and respiratory tract. Skin rash may occur if contaminated skin is exposed to sunlight. Can affect the nervous system, causing headache, fatigue, dizziness, vertigo (an illusion of movement), anorexia (loss of appetite). Long Term Exposure: Repeated or prolonged contact with skin may cause acne-like rash (chloracne), pruritus. May affect the liver, causing jaundice; liver necrosis. Points of Attack: Skin, liver, central nervous system.
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Pentachloronitrobenzene
Medical Surveillance: NIOSH lists the following tests: Liver function tests. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Up to 5 mg/m3: Sa* (APF 5 10) (any supplied-air respirator); or SCBAF (APF 5 50) (any selfcontained breathing apparatus with a full face-piece). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd,Pp (APF 5 10,000) (any NIOSH/MSHA- or European Standard EN 149-approved self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary, self-contained breathing apparatus operated in a pressure-demand or other positivepressure mode). Escape: GmFOv100 (APF 5 50) (any airpurifying, full-face-piece respirator (gas mask) with a chinstyle, front- or back-mounted organic vapor canister having an N100, R100, or P100 filter) or SCBAE (any appropriate escape-type, self-contained breathing apparatus). *Substance reported to cause eye irritation or damage; may require eye protection. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, wellventilated area away from strong oxidizers. Where possible, automatically transfer material from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers
involving the transfer of this chemical should be grounded and bonded. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Use HEPA vacuum or wet method to reduce dust during cleanup. Do not dry sweep. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible solid. Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Poisonous gases are produced in fire. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Reference New Jersey Department of Health and Senior Services. (December 1999). Hazardous Substances Fact Sheet: Pentachloronaphthalene. Trenton, NJ
Pentachloronitrobenzene
P:0230
Molecular Formula: C6Cl5NO2 Synonyms: Avicol (Pesticide); Bartilex; Batrilex; Benzene, pentachloronitro-; Botrilex; Brassicol; Brassicol 75; Brassicol earthcide; Brassicol super; Chinozan; Fartox; Folosan; Fomac 2; Fungichlor; GC 3944-3-4; Kobu; Kobutol; KP 2; Marisan forte; NCI-C00419; Nitropentachlorobenzene; Olipsan; Olpisan; PCNB; Pentachlornitrobenzol (German); Pentachloronitrobenzene; Pentagen; Phomasan; PKHNB; Quinosan; Quintocene; Quintoceno (Spanish); Quintozene; RTU1010; Saniclor 30; Terrachlor; Terraclor; Terraclor30 G; Terrafun; Tilcarex; Tripcnb; Tritisan CAS Registry Number: 82-68-8; (alt.) 39378-26-2 RTECS® Number: DA6650000
Pentachloronitrobenzene UN/NA & ERG Number: UN2811 (toxic solid, organic, n.o.s.)/154 EC Number: 201-435-0 [Annex I Index No.: 609-043-00-5] (quintozene) Regulatory Authority and Advisory Bodies Carcinogenicity: IARC: Animal Limited Evidence; Human No Adequate Data, not classifiable as carcinogenic to humans, Group 3, 1987; NCI: Carcinogenesis Studies (feed); no evidence: mouse; NTP: Carcinogenesis Studies (feed); no evidence: mouse. US EPA Gene-Tox Program, Negative: Host-mediated assay; In vitro UDS—human fibroblast; Negative: TRP reversion; S. cerevisiae—homozygosis; Negative/limited: Carcinogenicity—mouse/rat; Inconclusive: B. subtilis rec assay; E. coli polA without S9; Inconclusive: Histidine reversion—Ames test; Inconclusive: D. melanogaster sexlinked lethal. Banned or Severely Restricted (Germany, US) (UN).[13] US EPA, FIFRA, 1998 Status of Pesticides: Supported. Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. US EPA Hazardous Waste Number (RCRA No.): U185. RCRA, 40CFR261, Appendix 8 Hazardous Constituents. RCRA 40CFR268.48; 61FR15654, Universal Treatment Standards: Wastewater (mg/L), 0.055; Nonwastewater (mg/kg), 4.8. RCRA 40CFR264, Appendix 9; TSD Facilities Ground Water Monitoring List. Suggested test method(s) (PQL μg/L): 8270 (10). Reportable Quantity (RQ): 100 lb (45.4 kg). EPCRA Section 313 Form R de minimis concentration reporting level: 1.0%. European/International Regulations: Hazard Symbol: Xi, N; Risk phrases: R43; R50/53; Safety phrases: S2; S13; S24; S37; S60; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): No value assigned. Description: Pentachloronitrobenzene forms colorless needles. Technical-grade PCNB contains an average of 97.8% PCNB, 1.8% hexachlorobenzene (HCB), 0.4% 2,3,4,5-tetrachloronitrobenzene (TCNB), and less than 0.1% pentachlorobenzene. Molecular weight 5 295.32; Boiling point 5 328 C; Freezing/Melting point 5 146 C; Vapor pressure 5 1 3 10 2 4 mbar at 25 C. Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 0, Reactivity 0. Practically insoluble in water. Potential Exposure: Compound Description: Agricultural Chemical; Tumorigen, Mutagen; Reproductive Effector. Those engaged in the manufacture, formulation, and application of this soil fungicide and seed treatment chemical. Incompatibilities: Alkalis. Permissible Exposure Limits in Air ACGIH TLV®[1]: 0.5 mg/m3 TWA: not classifiable as a human carcinogen. Protective Action Criteria (PAC) TEEL-0: 0.5 mg/m3 PAC-1: 1.5 mg/m3
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PAC-2: 100 mg/m3 PAC-3: 500 mg/m3 Denmark: TWA 0.5 mg/m3, 1999; the Netherlands: MACTGG 0.5 mg/m3, 2003; Russia[35,43] set a MAC of 0.5 mg/m3 in work-place air and MAC values for ambient air in residential areas of 0.01 mg/m3 on a momentary basis and 0.006 mg/m3 on a daily average basis. A guideline in ambient air has been set[60] in Pennsylvania at 2.47 μg/m3. Determination in Water: Fish Tox 5 64.49856000 MATC (INTERMEDIATE). Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: May cause skin and eye irritation; sensitization with erythema, itching, and edema. A rebuttable presumption against registration of PCNB for pesticidal uses was issued on October 13, 1977 by EPA on the basis of oncogenicity. Long Term Exposure: There is limited evidence that this compound is an animal carcinogen. Human Tox 5 2.10000 ppb (HIGH). First Aid: Skin Contact[52]: Flood all areas of body that have contacted the substance with water. Do not wait to remove contaminated clothing; do it under the water stream. Use soap to help assure removal. Isolate contaminated clothing when removed to prevent contact by others. Eye Contact: Remove any contact lenses at once. Flush eyes well with copious quantities of water or normal saline for at least 2030 min. Seek medical attention. Inhalation: Leave contaminated area immediately; breathe fresh air. Proper respiratory protection must be supplied to any rescuers. If coughing, difficult breathing, or any other symptoms develop, seek medical attention at once, even if symptoms develop many hours after exposure. Ingestion: If convulsions are not present, give a glass or two of water or milk to dilute the substance. Assure that the person’s airway is unobstructed and contact a hospital or poison center immediately for advice on whether or not to induce vomiting. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuous-flow
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Pentachlorophenol
mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in pressure-demand or other positive-pressure mode. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in a refrigerator or a cool, dry place away from strong bases. A regulated, marked area should be established where this chemical is handled, used, or stored in compliance with OSHA Standard 1910.1045. Shipping: Toxic solids, organic, n.o.s. requires a shipping label of “POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 6.1 and Packing Group III. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Dampen spilled material with alcohol to avoid dust, then transfer material to a suitable container. Use absorbent dampened with alcohol to pick up remaining material. Wash surfaces well with soap and water. Seal all wastes in vapor-tight plastic bags for eventual disposal. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible solid. Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Poisonous gases are produced in fire. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant ($100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. In accordance with 40CFR165, follow recommendations for the disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by contacting your local or federal environmental control agency or by contacting your regional EPA office. It has
been observed that the product decomposes readily when burned with polyethylene. The compound is highly stable in soil in general, as would be expected on the basis of the polychlorinated aromatic structure.[22] References US Environmental Protection Agency. (April 30, 1980). Pentachloronitrobenzene, Health and Environmental Effects Profile No. 142. Washington, DC: Office of Solid Waste Sax, N. I. (Ed.). (1985). Dangerous Properties of Industrial Materials Report, 5, No. 3, 1116 US Environmental Protection Agency, Special Review and Reregistration Division Office of Pesticide Programs. (1998). Agency Status of Pesticides in Registration, Reregistration, and Special Review (Rainbow Report). Washington, DC New Jersey Department of Health and Senior Services. (January 2007). Hazardous Substances Fact Sheet: Chloronitrobenzenes (mixed isomers). Trenton, NJ
Pentachlorophenol
P:0240
Molecular Formula: C6HCl5O Common Formula: C6Cl5OH Synonyms: Chem-tol; Chlon; Chlorophen; Cryptogil ol; Dowcide 7; Dowicide 7; Dowicide EC-7; Dowicide G; Dow pentachlorophenol DP-2 antimicrobial; Dura treet II; Durotox; EP30; Fungifen; Glaze penta; Grundier arbezol; 1Hydroxypentachlorobenzene; Lauxtol; Lauxtol A; Liroprem; NCI-C54933; NCI-C55378; NCI-C56655; PCP; Penchlorol; Penta; Pentachlorofenol; Pentachlorophenate; 2,3,4,5,6-Pentachlorophenol; Pentachlorophenol, Dowicide EC-7; Pentachlorophenol, DP-2; Pentachlorophenol, technical; Pentachlorphenol (German); Pentaclorofenol (Spanish); Pentacon; Penta-Kil; Pentasol; Penwar; Peratox; Permacide; Permagard; Permasan; Permatox DP-2; Permatox penta; Permite; Phenol, pentachloro-; Pol nu; Preventol P; Priltox; Santobrite; Santophen; Santophen 20; Sinituho; Term-i-trol; Thompson’s wood fix; Weedone; Woodtreat A CAS Registry Number: 87-86-5 RTECS® Number: SM6300000 UN/NA & ERG Number: UN3155/154 EC Number: 201-778-6 [Annex I Index No.: 604-002-00-8] Regulatory Authority and Advisory Bodies Carcinogenicity: IARC: Animal Sufficient Evidence; Human Inadequate Evidence, possibly carcinogenic to humans, Group 2B, 1991; EPA: Sufficient evidence from animal studies; inadequate evidence or no useful data from epidemiologic studies; NCI: Carcinogenesis Studies (feed); clear evidence: mouse; (feed); equivocal evidence: rat. US EPA Gene-Tox Program, Positive: Cell transform.— SA7/SHE; S. cerevisiae gene conversion; Positive: S. cerevisiae—forward mutation; Negative: Host-mediated assay; Mouse spot test; Negative: Histidine reversion—Ames test; S. cerevisiae—homozygosis.
Pentachlorophenol US EPA, FIFRA, 1998 Status of Pesticides: Supported. Banned or Severely Restricted (several countries) (UN).[13] Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Clean Air Act: Hazardous Air Pollutants (Title I, Part A, Section 112). Clean Water Act: Section 311 Hazardous Substances/RQ 40CFR117.3 (same as CERCLA, see below); 40CFR401.15 Section 307 Toxic Pollutants; 40CFR423, Appendix A, Priority Pollutants; Section 313 Water Priority Chemicals (57FR41331, 9/9/92). US EPA Hazardous Waste Number (RCRA No.): D037. RCRA, 40CFR261, Appendix 8 Hazardous Constituents. RCRA Toxicity Characteristic (Section 261.24), Maximum. Concentration of Contaminants, regulatory level, 100 mg/L. RCRA 40CFR268.48; 61FR15654, Universal Treatment Standards: Wastewater (mg/L), 0.089; Nonwastewater (mg/kg), 7.4. RCRA 40CFR264, Appendix 9; TSD Facilities Ground Water Monitoring List. Suggested test method(s) (PQL μg/L): 8040 (5); 8270 (50). Safe Drinking Water Act: MCL, 0.001 mg/L; MCLG, zero; Regulated chemical (47 FR 9352). Reportable Quantity (RQ): 10 lb (4.54 kg) EPCRA Section 313 Form R de minimis concentration reporting level: 1.0%. US DOT Regulated Marine Pollutant (49CFR172.101, Appendix B), severe pollutant. Rotterdam Convention Annex III [Chemicals Subject to the Prior Informed Consent Procedure (PIC)] (as pentachlorophenol and its salts and esters). California Proposition 65 Chemical: Cancer 1/1/90. European/International Regulations: Hazard Symbol: T1, N; Risk phrases: R24/25; R26; R36/37/38; R40; R50/53; Safety phrases: S1/2; S22; S36/37; S45; S52; S60; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): 3—Severe hazard to waters. Description: Pentachlorophenol is a colorless to white crystalline solid. It has a benzene-like odor; pungent when hot. The odor threshold in water is 1600 μg/L and the taste threshold in water is 30 μg/L. Molecular weight 5 266.32; Specific gravity (H2O:1) 5 1.98; Boiling point 5 308.9 C (decomposes); Freezing/Melting point 5 190 C (anhydrous); Vapor pressure 5 0.0001 mmHg at 25 C. Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 0, Reactivity 0. Practically insoluble in water; solubility in water 5 0.001 at 20 C. Potential Exposure: Compound Description: Agricultural Chemical; Tumorigen, Mutagen; Reproductive Effector; Human Data; Primary Irritant. Pentachlorophenol (PCP) is a commercially produced bactericide, fungicide, and slimicide used primarily for the preservation of wood, wood products, and other materials. As a chlorinated hydrocarbon, its biological properties have also resulted in its use as an herbicide and molluscicide. Two groups can be expected to encounter
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the largest exposures. One involves the small number of employees involved in the manufacture of PCP. All of these are presently under industrial health surveillance programs. The second and larger group are the formulators and wood theaters. Exposure, hygiene and industrial health practices can be expected to vary from the small theaters to the larger companies. The principal use as a wood preservative results in both point source water contamination at manufacturing and wood preservation sites and, conceivably, nonpoint source water contamination through runoff wherever there are PCP-treated lumber products exposing PCP to soil. Incompatibilities: Reacts violently with strong oxidizers, acids, alkalis, and water. Permissible Exposure Limits in Air OSHA PEL: 0.5 mg/m3 TWA [skin]. NIOSH REL: 0.5 mg/m3 TWA [skin]. ACGIH TLV®[1]: 0.5 mg/m3 TWA [skin]; BEI: 2 mg[total PCP]/g creatinine in urine/prior to last shift of workweek; 5 mg [free PCP]/L in plasma/end-of-shift; confirmed animal carcinogen with unknown relevance to humans. NIOSH IDLH: 2.5 mg/m3. Protective Action Criteria (PAC) TEEL-0: 0.5 mg/m3 PAC-1: 2 mg/m3 PAC-2: 2.5 mg/m3 PAC-3: 2.5 mg/m3 DFG MAK: [skin] Carcinogen Category 2. Australia: TWA 0.5 mg/m3, [skin], 1993; Austria: [skin], carcinogen, 1999; Belgium: TWA 0.5 mg/m3, [skin], 1993; Denmark: TWA 0.005 ppm (0.05 mg/m3), [skin], 1999; Finland: TWA 0.5 mg/m3; STEL 1.5 mg/m3, [skin], 1999; France: VME 0.5 mg/m3, [skin], continuous carcinogen, 1999; Hungary: TWA 0.2 mg/m3; STEL 0.4 mg/m3, [skin], 1993; the Netherlands: MAC-TGG 0.06 mg/m3, [skin], 2003; Norway: TWA 0.05 ppm (0.5 mg/m3), 1999; Poland: MAC (TWA) 0.5 mg/m3; MAC (STEL) 1.5 mg/m3, 1999; Russia: STEL 0.1 mg/m3, [skin], 1993; Sweden: NGV 0.5 mg/m3, KTV 1.5 mg/m3, [skin], 1999; Switzerland: MAK-W 0.05 ppm (0.5 mg/m3); STEL 0.1 ppm, [skin], 1999; Turkey: TWA 0.5 mg/m3, [skin], 1993; United Kingdom: TWA 0.5 mg/m3; STEL 1.5 mg/m3, [skin], 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: confirmed animal carcinogen with unknown relevance to humans. The notation “skin” is added to indicate the possibility of cutaneous absorption. Russia[43] set a MAC of 0.1 mg/m3 in work-place air and a MAC in ambient basis. Several states have set guidelines or standards for Pentachlorophenol in ambient air[60] ranging from zero (North Carolina) to 0.034 μg/m3 (Massachusetts) to 1.67 μg/m3 (New York) to 5.0 μg/m3 (North Dakota and South Carolina) to 8.0 μg/m3 (Virginia) to 10.0 μg/m3 (Connecticut and South Dakota) to 12.0 μg/m3 (Nevada and Pennsylvania) to 25.64 μg/m3 (Kansas). Determination in Air: Use NIOSH (IV) Analytical Method #5512, Pentachlorophenol; in blood, #8001; in urine, #8303; OSHA Analytical Method 39.
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Pentachlorophenol
Determination in Water: Octanolwater coefficient: Log Kow 5 5.0. Permissible Concentration in Water: To protect freshwater aquatic life: 55 μg/L on an acute toxicity basis and 3.2 μg/L on a chronic basis. To protect saltwater aquatic life: 53 μg/ L on an acute basis and 34 μg/L on a chronic basis. To protect human health—1.010 μg/L is the criteria set by EPA based on toxicity data. A value of 30 μg/L is set on an organoleptic basis.[6] More recently, EPA[47] has developed a lifetime health advisory of 220 μg/L. WHO[35] has set a limit of 10 μg/L on pentachlorophenol in drinking water. Russia[43] set a MAC of 300 μg/L in water bodies used for domestic purposes. More recently, EPA has set a guideline of 200 μg/L for drinking water.[62] Several states have set guidelines for Pentachlorophenol in drinking water[61] ranging from 6 μg/L (Maine) to 30 μg/L (California) to 200 μg/L (Arizona) to 220 μg/L (Kansas and Minnesota). Determination in Water: Methylene chloride extraction followed by gas chromatography with electron capture or halogen specific detection (EPA Method 608) or gas chromatography plus mass spectrometry (EPA Method 625). Fish Tox 5 23.89351000 MATC (INTERMEDIATE) ppb. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Absorbed by the skin. Harmful Effects and Symptoms Short Term Exposure: Pentachlorophenol irritates the eyes, skin, and respiratory tract. May affect the cardiovascular system. Inhalation: Levels of 1 mg/m3 can cause severe irritation of the nose, throat, and lungs. Higher exposures can cause pulmonary edema, a medical emergency that can be delayed for several hours. This can cause death. Breathing dust or particulates tainted with pentachlorophenol can give rise to sneezing. Skin: A 0.04% solution can cause pain and inflammation at point of contact. Chloracne, a skin disorder, has been observed in workers in pentachlorophenol manufacturing plants and wood preserving operations. Profuse sweating and elevated temperature are symptoms of poisoning due to prolonged contact. Excessive skin exposure has caused human death. Eyes: Levels of 1 mg/m3 may be irritating and excessive contact can lead to loss of sight due to corneal damage. Ingestion: The lethal human dose is approximately equal to 1 teaspoon for a 150lb person. Ingestion of 48 oz followed by prompt emergency treatment still produced symptoms of poisoning which included rapid breathing followed by a decrease in breathing rate, abdominal pain, reduced blood pressure, excessive and slurred speech, and weakness. Long Term Exposure: Irritation of eyes, throat, nose, and upper lungs has been reported by individuals using pentachlorophenol as an insecticide for periods of a few years. Chemical acne has been associated with prolonged exposure to this compound. May affect the central nervous system, kidneys, liver, lungs. May be a carcinogen in humans. May damage the developing fetus. There is limited evidence that pentachlorophenol is a teratogen in animals. Tumors have
been detected in experimental animals. Human Tox 5 1.00000 ppb MCL (HIGH). Points of Attack: Eyes, skin, respiratory system, cardiovascular system, liver, kidneys, central nervous system. Cancer site in animals: liver. Medical Surveillance: NIOSH lists the following tests: whole blood (chemical/metabolite); blood plasma; blood plasma, end-of-shift; blood serum; urine (chemical/metabolite); urine (chemical/metabolite), end-of-workweek; urine (chemical/metabolite), prior-to-shift; urine (chemical/ metabolite), prior-to-last-shift-of-workweek. If symptoms develop or overexposure is suspected, the following may be useful: Urine test for pentachlorophenol. Liver and kidney function tests. Refer to the NIOSH Criteria Documents #78174 and #76-147, Manufacturing, formulating, and working safely with pesticides. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. Nitrile, polyvinyl chloride, and Tychem® (from E.I. du Pont de Nemours & Company) are among the recommended protective materials. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: 2.5 mg/m3: CcrOv95 (APF 5 10) [any air-purifying half-mask respirator with organic vapor cartridge(s) in combination with an N95, R95, or P95 filter. The following filters may also be used: N99, R99, P99, N100, R100, P100] or PaprOvHie (APF 5 25) (any powered air-purifying respirator with an organic vapor cartridge in combination with a high-efficiency particulate filter) or Sa
Pentachlorophenol (APF 5 10) (any supplied-air respirator) or SCBAF (APF 5 50) (any self-contained breathing apparatus with a full face-piece). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd,Pp (APF 5 10,000) (any self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary self-contained breathing apparatus operated in a pressuredemand or other positive-pressure mode). Escape: GmFOv100 (APF 5 50) (any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or backmounted organic vapor canister having an N100, R100, or P100 filter) or SCBAE (any appropriate escape-type, selfcontained breathing apparatus). Note: Substance reported to cause eye irritation or damage; may require eye protection. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Pentachlorophenol must be stored to avoid contact with strong oxidizers (such as chlorine, bromine, and fluorine) because violent reactions occur. Where possible, automatically transfer material from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of this chemical should be grounded and bonded. A regulated, marked area should be established where this chemical is handled, used, or stored in compliance with OSHA Standard 1910.1045. Shipping: Pentachlorophenol requires a shipping label of “POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 6.1 and Packing Group II. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: Extinguish fire using an agent suitable for type of surrounding fire (the material itself does not burn). Poisonous gases, including hydrogen chloride, dioxines, and chlorinated phenols, are produced in fire. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control
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agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant ($100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. In accordance with 40CFR165, follow recommendations for the disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by contacting your local or federal environmental control agency or by contacting your regional EPA office. Incineration (600900 C) coupled with adequate scrubbing and ash disposal facilities.[22] Alternatively pentachlorophenol in wastewaters, for example, may be recovered and recycled. References US Environmental Protection Agency. (1980). Pentachlorophenol: Ambient Water Quality Criteria. Washington, DC Rao, K. R. (Ed.). (1978). Pentachlorophenol: Chemistry, Pharmacology and Environmental Toxicology. Proceedings of a Symposium, Pensacola, FL, June 1977, New York, Plenum Press US Environmental Protection Agency. (April 30, 1980). Pentachlorophenol, Health and Environmental Effects Profile No. 143. Washington, DC: Office of Solid Waste Sax, N. I. (Ed.). Dangerous Properties of Industrial Materials Report, 3, No. 4, 7377 (1983) and 4, No. 3, 2426 (1984) US Public Health Service. (December 1988). Toxicological Profile for Pentachlorophenol. Atlanta, GA: Agency for Toxic Substances and Disease Registry US Environmental Protection Agency. (October 31, 1985). Chemical Hazard Information Profile: Pentachlorophenol. Washington, DC: Chemical Emergency Preparedness Program New York State Department of Health. (1986). Chemical Fact Sheet: Pentachlorophenol (Version 2 and Version 3). Albany, NY: Bureau of Toxic Substance Assessment US Environmental Protection Agency, Special Review and Reregistration Division Office of Pesticide Programs. (1998). Agency Status of Pesticides in Registration, Reregistration, and Special Review (Rainbow Report). Washington, DC New Jersey Department of Health and Senior Services. (August 2002). Hazardous Substances Fact Sheet: Pentachlorophenol. Trenton, NJ
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Pentaerythritol
Pentaerythritol
P:0250
Molecular Formula: C5H12O4 Common Formula: C(CH2OH)4 Synonyms: 2,2-bis(Hydroxymethyl)-1,3-propanediol; Methane tetramethylol; Monopentaerythritol; PE; Pentaerythrite; Tetrahydroxymethylmethane; Tetramethylolmethane CAS Registry Number: 115-77-5 RTECS® Number: RZ2490000 EC Number: 204-104-9 Regulatory Authority and Advisory Bodies Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. WGK (German Aquatic Hazard Class): 1—Low hazard to waters. Description: Pentaerythritol is a white crystalline solid. Molecular weight 5 136.17; Specific gravity (H2O:1) 5 1.38; Boiling point 5 (sublimes) 276 C at 30 mmHg; Freezing/ Melting point 5 (sublimes) 261 C; Vapor pressure 5 8 3 10 2 8 mmHg at 25 C. Hazard Identification (based on NFPA-704 M Rating System): Health 1, Flammability 2, Reactivity 0. Slightly soluble in water; 6% at 15 C. Potential Exposure: Pentaerythritol is used in coatings and stabilizers; in the formation of alkyd resins and varnishes. It is used as an intermediate in the manufacture of plasticizers, explosives (PETN), and pharmaceuticals. Incompatibilities: Organic acids, oxidizers. Explosive compound is formed when a mixture of PE and thiophosphoryl chloride is heated. Permissible Exposure Limits in Air OSHA PEL: 15 mg/m3 (total inhalable dust) TWA; 5 mg/ m3 TWA, respirable fraction. NIOSH REL: 10 mg/m3 (total inhalable dust) TWA; 5 mg/ m3 TWA, respirable fraction. ACGIH TLV®[1]: 10 mg/m3 TWA. Protective Action Criteria (PAC) TEEL-0: 15 mg/m3 PAC-1: 30 mg/m3 PAC-2: 50 mg/m3 PAC-3: 500 mg/m3 Australia: TWA 10 mg/m3, 1993; Belgium: TWA 10 mg/ m3, 1993; Finland: TWA 10 mg/m3; STEL 20 mg/m3, 1999; France: VME 10 mg/m3, 1999; United Kingdom: TWA 10 mg/m3; STEL 20 mg/m3, total inhalable dust; TWA 4 mg/m3, respirable dust, 2000; the Netherlands: MACTGG 10 mg/m3 (total dust), 2003; the Netherlands: MACTGG 5 mg/m3 (respirable dust), 2003; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: TWA 10 mg/m3. States which have set guidelines or standards for pentaerythritol in ambient air[60] include Virginia at 80 μg/m3 and Connecticut at 300 μg/m3. Determination in Air: Use NIOSH IV Method #0500, total dust; Method #0600 (respirable dust), Particulates NOR.
Permissible Concentration in Water: Russia[43] set a MAC of 0.1 mg/L in water bodies used for domestic purposes. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Irritates the eyes and respiratory system. Feeding studies using human volunteers showed that 85% of Pentaerythritol fed was eliminated unchanged in the urine within 30 h. There are, in general, no significant effects on health by common routes of exposure even at abnormal use concentrations. Points of Attack: Eyes, respiratory system. Medical Surveillance: There is no special test for this chemical. However, if illness occurs or overexposure is suspected, medical attention is recommended. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Use dust respirator. Storage: Color Code—Green: General storage may be used. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, well-ventilated area away from organic acids, oxidizers. Shipping: Not regulated. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially
Pentaerythritol tetranitrate contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible solid. Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Poisonous gases are produced in fire. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode.
Pentaerythritol tetranitrate
P:0255
Molecular Formula: C5H8N4O12 Common Formula: C(CH2ONO2)4 Synonyms: Angicap; Angitet; Cardiacap; 1,3-Dinitrato-2,2bis(nitratomethyl)propane; Nitropenta; Pentaerythrite tetranitrate; Pentaerithrityl tetranitrate; Pentaerithrityltetranitrat (German); Pentrita (Spanish); PETN; 1,3-Propanediol,2,2bis[(nitrooxy) methyl]-, dinitrate (ester); Tetranitrato de pentaeritritilo (Spanish); Te´tranitrate de pentaerithrityle (French); Vasitol; Vasodiatol CAS Registry Number: 78-11-5; (alt.) 103842-90-6; (alt.) 108736-71-6 RTECS®Number: RZ2620000 UN/NA & ERG Number: UN3344 (Pentaerythrite tetranitrate mixture, desensitized, solid, n.o.s. with .10% but not .20% PETN, by mass)/113; UN0150 (Pentaerythrite tetranitrate, wetted or Pentaerythritol tetranitrate, wetted, or PETN, wetted or Pentaerythrite tetranitrate, or Pentaerythritol tetranitrate or PETN, desensitized)/112 EC Number: 201-084-3 Regulatory Authority and Advisory Bodies Department of Homeland Security Screening Threshold Quantity (pounds): Release hazard 5000 (commercial grade); Theft hazard 400 (commercial grade). Not listed under California Proposition 65. Chemicals Subject to TSCA 12(b) Export Notification Requirements, Section 4 (1%). European/International Regulations: Hazard Symbol: E; Risk phrases: R3; Safety phrases: S2; S35 (see Appendix 4). WGK (German Aquatic Hazard Class): No value assigned.
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Description: Pentaerythrite tetranitrate (PETN) is a high explosive, especially when dry. PETN is a sand-like, white crystalline solid. Practically odorless. Molecular weight 5 316.17; Boiling point 5 205215 C (explodes); Vapor pressure 5 negligible; 1.04 3 10 2 10 mmHg at 25 C; 1.035 3 10 2 10 mmHg at 25 C. Density 1.751.77 g/cm3. Freezing/Melting point 5 138140 C. Autoignition temperature 5 (explodes) 210 C. Hazard Identification (based on NFPA-704 M Rating System): Health 2; Flammability, 2; Reactivity, 4. Solubility in water 5 4.3 mg/100 g at 25 C. The principal hazard from PETN is blast from sudden and abrupt explosion; not from ruptured or bursting container fragments or rocketing projectiles. Potential Exposure: Compound Description: Tumorigen, Drug, Mutagen, Human Data. First introduced following WWII, PETN shares the same chemical family as nitroglycerine. It is 70% more powerful than TNT.[NYT] Used in the manufacture of fuses for detonation and explosive specialties, including the plastic explosive, Semtex, and in blasting caps. PETN is also used as a medical vasodilator to lower blood pressure by widening blood vessels to improve blood flow. PRTN has been used in terrorism attempts in 2001 by the so-called “shoe bomber,” in 2009 by the “underwear bomber,” and most recently in October 2010, hidden in printer cartridges being shipped internationally by passenger jet. Incompatibilities: Normally stable, PETN does not easily explode when dropped or set on fire (rapid heating can cause detonation when heated to 210 C). Nevertheless, PETN is a dangerous high explosive and a strong oxidizer. PETN normally requires a blasting cap or other kind of detonator but may decompose explosively from concussion, shock, friction, static charges. Contact with reducing agents (e.g., zinc, alkaline metals) may cause explosion. Keep away from combustible materials, other oxidizers (e.g., nitrates, permanganates). Contact with sulfur trioxide may cause detonation. May explode in the presence of strong bases (i.e., sodium or potassium hydroxide). May react with heavy metals. Permissible Exposure Limits in Air Protective Action Criteria (PAC) TEEL-0: 0.015 mg/m3 PAC-1: 0.05 mg/m3 PAC-2: 0.35 mg/m3 PAC-3: 500 mg/m3 If material is mixed with TNT, see entry T:0920. Determination in Air: NIOSH method not established. If material is mixed with TNT, see entry T:0920. Determination in Water: Octanolwater coefficient: Log Kow 5 1.60. Routes of Entry: Inhalation of dust, fume, or vapor; ingestion of dust; percutaneous absorption from dust, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Corrosive and highly irritating. Target organs are the skin and heart. Contact irritates the
2078
Pentaerythritol tetranitrate
eyes, nose, and throat. Can penetrate the skin. Exposure can cause red eyes, dizziness, irritability, headache, convulsions, nausea, vomiting. PETN is a vasodilator and can affect the cardiovascular system, resulting in widening of blood vessels and the lowering of blood pressure. Medical care is advised. Long Term Exposure: Lowest published toxic dose (oral, man): 1669 mg/kg/8 year—continuous. [British Journal of Dermatology (87, 498, 1972)]. Medical Surveillance: If material is mixed with TNT, see entry T:0920. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. Polyvinyl chloride is among the recommended protective materials. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless fullface-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. The Webster skin test (colorimetric tests with alcoholic sodium hydroxide) or indicator soap should be used to make sure workers have washed all PETN off their skins. Respirator Selection: 95XQ (APF 5 10) [any particulate respirator equipped with an N95, R95, or P95 filter (including N95, R95, and P95 filtering face-pieces) except quartermask respirators. The following filters may also be used: N99, R99, P99, N100, R100, P100]; or any air-purifying full-face-piece respirator equipped with an N95, R95, or P95 filter. The following filters may also be used: N99, R99, P99, N100, R100, P100; or PaprHie (APF 5 25) (any powered, air-purifying respirator with a high-efficiency particulate filter) or PaprTHie (APF 5 50) (any powered, airpurifying respirator with a tight-fitting face-piece and a high-efficiency particulate filter) or any supplied-air respirator with a full face-piece that is operated in a pressuredemand or other positive-pressure mode. Emergency or planned entry into unknown concentrations or IDLH conditions: SaF: Pd,Pp: ASCBA (any supplied-air respirator that
has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: 100F (APF 5 50) (any air-purifying, full-face-piece respirator with an N100, R100, or P100 filter) or SCBAE (any appropriate escape-type, self-contained breathing apparatus). Storage: An explosive and a strong oxidizer. Color Code— Red Stripe: Flammability Hazard: Store in a explosion-proof refrigerator and keep away from reducing agents.[52] Store in a cool, dark place in a airtight container, separately from all other flammable materials. Unless specified by manufacturer, store between 15 C and 30 C. Protect from light. Prior to working with this chemical you should be trained on its proper handling and storage. Keep material wet with water and treat as an explosive. Keep away from heat, sources of ignition, metal, nitric acid, and reducing materials. Protect containers from shock. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. A regulated, marked area should be established where this chemical is handled, used, or stored in compliance with OSHA Standard 1910.1045. Shipping: Pentaerythrite tetranitrate mixture, desensitized, solid, n.o.s. with .10% but not .20% PETN, by mass. Must be labeled “FLAMMABLE SOLID.” This falls into Hazard Class 4.1 and Packing Group II. Pentaerythrite tetranitrate, wetted or Pentaerythritol tetranitrate, wetted, or PETN, wetted or Pentaerythrite tetranitrate, or Pentaerythritol tetranitrate or PETN, desensitized must be labeled “EXPLOSIVE 1.1D.” It falls in Hazard Class 1.1D and Packing Group II. Air transport in passenger and cargo planes is FORBIDDEN. Spill Handling: Seek expert help or contact manufacturer. Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Dampen spilled material with water to avoid dust. Do not wash material to sewer. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Collect waste material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: Seek expert help or contact manufacturer. This chemical is a dangerously explosive solid and a strong oxidizer. It will increase the activity of an existing fire. The major hazard from PETN is the blast from sudden and abrupt explosion; not necessarily from ruptured or bursting container fragments or rocketing projectiles. When heated to decomposition, this material emits highly toxic nitrogen oxide fumes. If material is on fire and conditions
Pentane permit, do not extinguish. Evacuate area and let burn. Cool exposures using unattended monitors. If fire must be extinguished, use any agent appropriate for the burning material. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. References New Jersey Department of Health and Senior Services. (October 2001). Hazardous Substances Fact Sheet: Pentaerythrite Tetranitrate. Trenton, NJ Chang, K. (November 31, 2010). The New York Times news article, Explosive on Planes Was Used in Past Plots. New York, NY
Pentane
P:0260
Molecular Formula: C5H12 Synonyms: Amyl hydride; Normalpentane; n-Pentane; normal-Pentane; n-Pentano (Spanish); Skellysolve-A CAS Registry Number: 109-66-0 RTECS® Number: RZ9450000 UN/NA & ERG Number: UN1265/128 EC Number: 203-692-4 [Annex I Index No.: 601-006-00-1] Regulatory Authority and Advisory Bodies Department of Homeland Security Screening Threshold Quantity (pounds): Release hazard 10,000 ($1.00% concentration). Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Clean Air Act: Accidental Release Prevention/Flammable Substances, (Section 112[r], Table 3), TQ 5 10,000 lb (4540 kg). Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: Hazard Symbol: F, Xn, N; Risk phrases: R12; R51/53; R65; R66; R67; Safety phrases: S2; S9; S16; S29; S33 (see Appendix 4). WGK (German Aquatic Hazard Class): 2—Hazard to waters. Description: Pentane is a colorless liquid. Gas above 36 C. Gasoline-like odor. Molecular weight 5 72.17; Specific gravity (H2O:1) 5 0.63; Boiling point 5 36 C; Freezing/ Melting point 5 129 C; Vapor pressure 5 420 mmHg at 25 C; Flash point 5 49.4 C (cc); Autoignition temperature 5 260 C; also listed at 284 and 309 C.
2079
Explosive limits: LEL 5 1.4%; UEL 5 7.8%. Hazard Identification (based on NFPA-704 M Rating System): Health 1, Flammability 4, Reactivity 0. Slightly soluble in water. Potential Exposure: Compound Description: Drug, Human Data. Pentane is used in the manufacture of ice, low-temperature thermometers, in solvent extraction processes, as a blowing agent in plastics, as a fuel, as a chemical intermediate (e.g., amylchlorides). Incompatibilities: Reacts with strong oxidizers. Attacks some plastics, rubbers, and coatings. Permissible Exposure Limits in Air Conversion factor: 1 ppm 5 2.95 mg/m3 at 25 C & 1 atm. OSHA PEL: 1000 ppm/2950 mg/m3 TWA. NIOSH REL: 120 ppm/350 mg/m3 TWA; 610 ppm/ 1800 mg/m3 [15 min] Ceiling Concentration. ACGIH TLV®[1]: 600 ppm/1770 TWA. NIOSH IDLH: 1500 ppm [LEL]. Protective Action Criteria (PAC) TEEL-0: 120 ppm PAC-1: 120 ppm PAC-2: 610 ppm PAC-3: 1500 ppm DFG MAK: 1000 ppm/3000 mg/m3 TWA; Peak Limitation Category II(2); Pregnancy Risk Group C. Australia: TWA 600 ppm (1800 mg/m3); STEL 750 ppm, 1993; Austria: MAK 600 ppm (1899 mg/m3), 1999; Belgium: TWA 600 ppm (1770 mg/m3); STEL 750 ppm (2210 mg/m3), 1993; Denmark: TWA 500 ppm (1500 mg/ m3), 1999; Finland: TWA 500 ppm (1500 mg/m3); STEL 625 ppm (1800 mg/m3), 1999; France: VME 600 ppm (1800 mg/m3), 1999; Hungary: TWA 500 mg/m3; STEL 1500 mg/m3, 1993; the Netherlands: MAC-TGG 1800 mg/ m3, 2003; the Philippines: TWA 1000 ppm (2950 mg/m3), 1993; Poland: MAC (TWA) 1800 mg/m3; MAC (STEL) 2300 mg/m3, 1999; Russia: TWA 300 ppm; STEL 300 mg/ m3, 1993; Sweden: NGV 600 ppm (1800 mg/m3), KTV 750 ppm (2000 mg/m3), 1999; Switzerland: MAK-W 600 ppm (1800 mg/m3), 1999; Turkey: TWA 1000 ppm (2950 mg/m3), 1993; United Kingdom: LTEL 600 ppm (1800 mg/m3); STEL 750 ppm, 1993; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: TWA 600 ppm. Russia[43] set a MAC of 100 mg/m3 in ambient air in residential areas on a momentary basis and 25 mg/m3 on a daily average basis. Several states have set guidelines or standards for pentane in ambient air[60] ranging from 7.0 mg/m3 (Connecticut) to 18.022.5 mg/m3 (North Dakota) to 30.0 mg/m3 (Virginia) to 42.857 mg/m3 (Nevada). Determination in Air: Use NIOSH Analytical Method #1500, Hydrocarbons, BP 36-126 C; #2549, Volatile organic compounds.[18] Determination in Water: Octanolwater coefficient: Log Kow 5 3.4. Routes of Entry: Inhalation, ingestion, skin and/or eye contact.
2080
Pentane
Harmful Effects and Symptoms Short Term Exposure: Pentane can affect you when breathed in. Exposure can cause lightheadedness and dizziness and may cause you to pass out. It may damage the nervous system, causing numbness, “pins and needles,” and weakness in the arms and legs. Skin contact may cause rash and a burning sensation. Long Term Exposure: Repeated or prolonged contact can cause dry, cracked skin. Points of Attack: Eyes, skin, respiratory system, and central nervous system. Medical Surveillance: If symptoms develop or overexposure is suspected, the following may be useful: examination of the nervous system. Nerve conduction studies should be considered. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. Viton is among the recommended protective materials. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: NIOSH: 1200 ppm: Sa (APF 5 10) (any supplied-air respirator). 1500 ppm: Sa:Cf (APF 5 25) (any supplied-air respirator operated in a continuous-flow mode) or SCBAF (APF 5 50) (any self-contained breathing apparatus with a full face-piece) or SaF (APF 5 50) (any supplied-air respirator with a full face-piece). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd,Pp (APF 5 10,000) (any self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary self-contained breathing apparatus operated in a pressure-demand or other positive-pressure
mode). Escape: GmFOv (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or back-mounted organic vapor canister] or SCBAE (any appropriate escape-type, self-contained breathing apparatus). Storage: Color Code—Red: Flammability Hazard: Store in a flammable liquid storage area or approved cabinet away from ignition sources and corrosive and reactive materials. Prior to working with this chemical you should be trained on its proper handling and storage. Before entering confined space where this chemical may be present, check to make sure that an explosive concentration is not a danger. Pentane must be stored to avoid contact with strong oxidizers (such as chlorine and bromine) because violent reactions occur. Store in tightly closed containers in a cool, well-ventilated area away from heat. Sources of ignition, such as smoking and open flames, are prohibited where pentane is handled, used, or stored. Metal containers involving the transfer of 5 gallons or more of pentane should be grounded and bonded. Drums must be equipped with selfclosing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of pentane. Shipping: Pentanes require a label of “FLAMMABLE LIQUID.” They fall in Hazard Class 3 and Packing Group I. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Establish forced ventilation to keep levels below explosive limit. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Oil-skimming equipment and sorbent foams can be applied to slick if done immediately. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a flammable liquid. Poisonous gases are produced in fire. Use dry chemical, carbon dioxide, or alcohol foam extinguishers. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location,
2,4-Pentanedione use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Dissolve or mix the material with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber. All federal, state, and local environmental regulations must be observed. References National Institute for Occupational Safety and Health. (1977). Criteria for a Recommended Standard: Occupational Exposure to Alkanes, NIOSH Document No. 77-151. Washington, DC New Jersey Department of Health and Senior Services. (February 2000). Hazardous Substances Fact Sheet: Pentane. Trenton, NJ
2,4-Pentanedione
P:0270
Molecular Formula: C5H8O2 Common Formula: CH3COCH2COCH3 Synonyms: Acetoacetone; Acetyl acetone; Diacetylmethane; Pentane-2,4-dione; 2-Propanone, acetyl CAS Registry Number: 123-54-6; 81235-32-7 RTECS® Number: SA1925000 UN/NA & ERG Number: UN2310/131 EC Number: 204-634-0 [Annex I Index No.: 606-029-00-0] Regulatory Authority and Advisory Bodies Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations (23-54-6): Hazard Symbol: Xn; Risk phrases: R10; R22; Safety phrases: S2; S21; S23; S24/25 (see Appendix 4). WGK (German Aquatic Hazard Class): 1—Low hazard to waters. Description: 2,4-Pentanedione is a colorless to yellowish liquid with a sour, rancid odor. The odor threshold is 0.01 ppm. Molecular weight 5 100.13; Boiling point 5 139 C; Freezing/Melting point 5 23 C; Flash point 5 34 C; Autoignition temperature 5 340 C. Explosive limits: LEL 5 2.4%; UEL 5 11.6%. Hazard Identification (based on NFPA-704 M Rating System): Health 2, Flammability 2, Reactivity 0. Soluble in water. Potential Exposure: Acetoacetic acid derivative. Compound Description: Agricultural Chemical; Mutagen; Reproductive Effector; Primary Irritant. 2,4-Pentanedione is used in gasoline and lubricant additives, fungicides, insecticides, and colors manufacture; as a chemical intermediate and in the manufacture of metal chelates.
2081
Incompatibilities: Oxidizing material, bases, reducing agents, halogens, aliphatic amines, alkanolamines, organic acids, isocyanates. Light may cause polymerization. Permissible Exposure Limits in Air ACGIH TLV®[1]: (2010 Notice of intended change) 25 ppm TWA [skin]. Protective Action Criteria (PAC) TEEL-0: 20 ppm PAC-1: 50 ppm PAC-2: 100 ppm PAC-3: 100 ppm DFG MAK: 20 ppm/83 mg/m3 TWA; Peak Limitation Category II(2) [skin]; Pregnancy Risk Group C. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Irritates the eyes, skin, and respiratory tract. Eye irritation may be severe. May affect the nervous system. If inhaled, will cause dizziness, coughing, headaches, convulsions, loss of consciousness, and possible death. In addition, to neuropathy, 2,4-pentanedione causes thymic atrophy; it complexes with and inhibits the activities of oxidizing enzymes; it causes minor to severe eye injury and minor to moderate skin irritation in animals; and it has caused contact urticaria and allergic contact dermatitis in humans. Long Term Exposure: Repeated or prolonged contact may cause skin sensitization and allergy. High exposure may affect the brain. May affect the lungs, thymus, central nervous system. There is limited evidence of reproductive damage and mutations. Points of Attack: Skin, brain, lungs, central nervous system, thymus. Medical Surveillance: Evaluation by a qualified allergist. Evaluation of brain effects. Thymus function tests. Consider chest X-ray following acute overexposure. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be
2082
1-Pentene
worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in pressure-demand or other positive-pressure mode. Storage: Color Code—Red: Flammability Hazard: Store in a flammable liquid storage area or approved cabinet away from ignition sources and corrosive and reactive materials. Prior to working with this chemical you should be trained on its proper handling and storage. Before entering confined space where this chemical may be present, check to make sure that an explosive concentration is not a danger. Store in stainless steel containers away from oxidizers, reducing agents, bases. Where possible, automatically pump liquid from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of 5 gallons or more of this chemical should be grounded and bonded. Drums must be equipped with self-closing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: Pentane-2,4-dione requires a shipping label of “FLAMMABLE LIQUID.” It falls in Hazard Class 3 and Packing Group III. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Establish forced ventilation to keep levels below explosive limit. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a flammable liquid. Poisonous gases are produced in fire. Use dry chemical,
carbon dioxide, alcohol foam, or polymer foam extinguishers. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Dissolve or mix the material with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber. All federal, state, and local environmental regulations must be observed. References Sax, N. I. (Ed.). (1981). Dangerous Properties of Industrial Materials Report, 1, No. 7, 2526 (as Acetylacetone) US Environmental Protection Agency. (August 25, 1988). Chemical Hazard Information Profile Draft Report: Pentanedione. Washington, DC: Office of Toxic Substances New Jersey Department of Health and Senior Services. (August 1999). Hazardous Substances Fact Sheet: Pentane2,4-dione. Trenton, NJ
1-Pentene
P:0280
Molecular Formula: C5H10 Common Formula: CH3(CH2)2CHQCH2 Synonyms: Amylene; α-n-Amylene; Pentene; Pentylene; Propylethylene CAS Registry Number: 109-67-1; (alt.) 25377-72-4 RTECS®Number: SB2179000 UN/NA & ERG Number: UN1108/128 EC Number: 246-916-6 Regulatory Authority and Advisory Bodies Department of Homeland Security Screening Threshold Quantity (pounds): Release hazard 10,000 ($1.00% concentration). Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. WGK (German Aquatic Hazard Class): No value assigned. Description: Pentene is a colorless liquid. Molecular weight 5 70.15; Boiling point 5 30 C; Vapor pressure 5 60.8 mmHg at 20 C; Flash point 5 18 C; Autoignition
1-Pentene temperature 5 276 C. Explosive limits: LEL 5 1.5%; UEL 5 8.7%. Hazard Identification (based on NFPA-704 M Rating System): Health 1, Flammability 4, Reactivity 1. Potential Exposure: Workers in petroleum refineries and petrochemical plants. Incompatibilities: Strong oxidants. Permissible Exposure Limits in Air Protective Action Criteria (PAC) 109-67-1 TEEL-0: 300 ppm PAC-1: 750 ppm PAC-2: 6000 ppm PAC-3: 75,000 ppm Russia[43] set a MAC for amylene in ambient air of residential areas at 1.5 mg/m3 both on a momentary and a daily average basis. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Simple asphyxiant. Narcotic in high concentrations. May affect central nervous system. Moderately toxic by oral and inhalation routes. Long Term Exposure: There is no special test for this chemical. However, if illness occurs or overexposure is suspected, medical attention is recommended. Points of Attack: Skin, eyes, respiratory tract, and nervous system. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Use protective gloves and safety goggles. Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a
2083
NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in pressure-demand or other positive-pressure mode. Storage: Color Code—Red: Flammability Hazard: Store in a flammable liquid storage area or approved cabinet away from ignition sources and corrosive and reactive materials. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, well-ventilated area away from oxidizers. Before entering confined space where this chemical may be present, check to make sure that an explosive concentration is not a danger. Where possible, automatically pump liquid from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of 5 gallons or more of this chemical should be grounded and bonded. Drums must be equipped with self-closing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosionproof electrical equipment and fittings. Shipping: 1-Pentene requires a shipping label of “FLAMMABLE LIQUID.” It falls in Hazard Class 3 and Packing Group I. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Establish forced ventilation to keep levels below explosive limit. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a flammable liquid. Poisonous gases are produced in fire. Use dry chemical, carbon dioxide, or alcohol foam extinguishers. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many
2084
Peracetic acid
directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Dissolve or mix the material with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber. All federal, state, and local environmental regulations must be observed. References Sax, N. I. (Ed.). Dangerous Properties of Industrial Materials Report, 2, No. 6, 6971 (1982) and 3, No. 2, 5657 (1983) New Jersey Department of Health and Senior Services. (March 2007). Hazardous Substances Fact Sheet: nPentene. Trenton, NJ
Peracetic acid
P:0290
Molecular Formula: C2H4O3 Common Formula: CH3COOOH Synonyms: Acetic peroxide; Acetyl hydroperoxide; Acide peracetique (French); Acido peracetico (Spanish); Desoxon 1; Estosteril; Ethaneperoxoic acid; Hydrogen peroxide and peroxyacetic acid mixture; Hydroperoxide, acetyl; Monoperacetic acid; Osbon AC; Oxymaster; PAA; Peroxyacetic acid; Proxitane; Proxitane 4002 CAS Registry Number: 79-21-0 RTECS® Number: SD8750000 UN/NA & ERG Number: UN3105 [Organic peroxide type D, liquid (stabilized)]/145; UN3109 [Organic Peroxide Type F, Liquid (with #17% Peracetic Acid with # 26% Hydrogen Peroxide)]/145 EC Number: 201-186-8 [Annex I Index No.: 607-094-00-8] Regulatory Authority and Advisory Bodies Department of Homeland Security Screening Threshold Quantity (pounds): Release hazard 10,000 ($1.00% concentration). US EPA, FIFRA 1998 Status of Pesticides: RED completed. Highly Reactive Substance and Explosive (World Bank).[15] Clean Air Act: Accidental Release Prevention/Flammable Substances, (Section 112[r], Table 3), TQ 5 10,000 lb (4540 kg). Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 500 lb (227 kg).
Reportable Quantity (RQ): 500 lb (227 kg). EPCRA Section 313 Form R de minimis concentration reporting level: 1.0%. Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: Hazard Symbol: O, C, N; Risk phrases: R7; R10; R20/21/22; R35; R50; Safety phrases: S1/2; S3/7; S14; S36/37/39; S45; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): 2—Hazard to waters. Description: Peracetic acid is a colorless liquid. Transported and stored in diluted solution with acetic acid and hydrogen peroxide to prevent explosion. Molecular weight 5 76.06; Specific gravity (H2O:1) 5 1.2; Boiling point 5 105 C (violent decomposition at 110 C); Freezing/ Melting point 5 0.1 C; Flash point 5 41.3 C (oc); 56 C (32% in dilute acetic acid and ,6% hydrogen peroxide); Autoignition temperature 5 198 C; Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 2, Reactivity 2 (Oxidizer). Soluble in water. Potential Exposure: Compound Description: Agricultural Chemical; Tumorigen, Primary Irritant. This compound is used as polymerization initiator, curing agent, and crosslinking agent; as bactericide and fungicide, especially in food processing; a reagent in making caprolactam and glycerol; an oxidant for preparing epoxy compounds; a bleaching agent; a sterilizing agent; and a polymerization catalyst for polyester resins. Incompatibilities: This material is a powerful oxidizer. Thermally unstable, it decomposes violently at 110 C. Concentrated material is shock- and friction-sensitive. May explode if concentration exceeds 56% of carrier, due to evaporation. Isolate from other stored material, particularly accelerators, oxidizers, organic or combustible materials, olefins, hydrogen peroxide, acetic anhydride, reducing substances. Keep away from acids, alkalis, heavy metals, organic materials. Permissible Exposure Limits in Air Protective Action Criteria (PAC)* TEEL-0: 0.15 mg/m3 PAC-1: 0.52 mg/m3 PAC-2: 1.6 mg/m3 PAC-3: 15 mg/m3 *AEGLs (Acute Emergency Guideline Levels) & ERPGs (Emergency Response Planning Guideline) are in bold face. DFG MAK: Carcinogen Category 3B; See section X(a). Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Eye contact can cause severe irritation and burns; may cause permanent damage. Irritates the respiratory tract. Contact may burn the skin. Higher exposures can cause pulmonary edema, a medical emergency that can be delayed for several hours. This can cause death.
Peracetic acid Signs and symptoms of acute ingestion of peracetic acid may include corrosion of mucous membranes of mouth, throat, and esophagus with immediate pain and dysphagia (difficulty in swallowing); ingestion may cause gastrointestinal tract irritation. This is a very toxic compound. The probable oral lethal dose for humans is 50500 mg/kg or between 1 teaspoon and 1 oz for a 150-lb person. Long Term Exposure: There is limited evidence that peracetic acid causes cancer in animals. It may cause cancer of the lungs. High or repeated exposure may affect the liver and kidneys. Points of Attack: Liver, kidneys, lungs. Medical Surveillance: Liver and kidney function tests. Consider chest X-ray following acute overexposure. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. If victim is conscious, administer water or milk. Do not induce vomiting. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. Butyl rubber and Viton are recommended. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Where there is no REL, at any detectable concentration: Sa:Cf (APF 5 25) (any suppliedair respirator operated in a continuous-flow mode) or PaprOv (APF 5 25) [any powered, air-purifying respirator with organic vapor cartridge(s)]; CcrFOv (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or back-mounted acid gas canister] or GmFOv (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or back-mounted organic vapor canister] or SCBAF (APF 5 50) (any selfcontained breathing apparatus with a full face-piece) or SaF (APF 5 50) (any supplied-air respirator with a full face-
2085
piece). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd,Pp (APF 5 10,000) (any self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary self-contained breathing apparatus operated in a pressuredemand or other positive-pressure mode). Escape: GmFOv (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or back-mounted organic vapor canister] or SCBAE (any appropriate escapetype, self-contained breathing apparatus). Storage: Color Code—Red Stripe: Flammability Hazard: Do not store in the same area as other flammable materials. Prior to working with this chemical you should be trained on its proper handling and storage. Keep in a cool, well-ventilated area, separated from organic and combustible materials. Where possible, automatically pump liquid from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of 5 gallons or more of this chemical should be grounded and bonded. Drums must be equipped with self-closing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. See OSHA Standard 1910.104 and NFPA 43A Code for the Storage of Liquid and Solid Oxidizers for detailed handling and storage regulations. Shipping: Organic peroxide type D, liquid, requires a shipping label of “ORGANIC PEROXIDE.” They fall in DOT Hazard Class 5.2 and Packing Group I. Organic peroxide type F, liquid, requires a shipping label of “Organic Peroxide Type F, Liquid (with ,5 17% Peracetic Acid with ,5 26% Hydrogen Peroxide).” They fall in DOT Hazard Class 5.2 and Packing Group II. Shipment of solutions with .43% peracetic acid is FORBIDDEN under any conditions. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Ventilate area of spill or leak. Avoid breathing vapors. Do not touch the spilled material; shut off all ignition sources and stop the leak if this can be done without risk. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Do not use spark-generating metals or organic materials for sweeping up or handling spilled material. Dispose of the absorbed peroxyacetic acid solution, in small quantities at a time, by placing it on the ground in a remote outdoor area and igniting with a long torch. Empty containers
2086
Perchloromethyl mercaptan
should be washed with a 10% sodium hydroxide solution. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible liquid and a powerful oxidizer that can increase the activity of an existing fire. It explodes at 230 F/110 C and is shock sensitive, particularly if organic solvents are used in place of acetic acid as a carrier. Poisonous gases are produced in fire. Fight fires from an explosion-resistant location. In advanced or massive fires, area should be evacuated. For small fires: use dry chemical, carbon dioxide, water spray, or foam. For large fires: flood area with water. If fire occurs in the vicinity of this compound, water should be used to keep containers cool. Cleanup and salvage operations should not be attempted until all of the peroxyacetic acid solution has cooled completely. Keep unnecessary people away; wear self-contained breathing apparatus and full protective clothing. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. References US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Peracetic Acid. Washington, DC: Chemical Emergency Preparedness Program New York State Department of Health. (April 1986). Chemical Fact Sheet: Peracetic Acid. Albany, NY: Bureau of Toxic Substance Assessment New Jersey Department of Health and Senior Services. (October 2004). Hazardous Substances Fact Sheet: Peroxyacetic Acid. Trenton, NJ
Perchloromethyl mercaptan
P:0300
Molecular Formula: CCl4S Common Formula: CCl3SCl Synonyms: Clairsit; Mercaptan methylique perchlore (French); Perchloromethanethiol; PMM; Trichloromethane sulfenyl chloride; Trichloromethylsulfenyl chloride; Trichloromethyl sulfur chloride; Trichloromethylsulphenyl chloride PCV CAS Registry Number: 594-42-3 RTECS® Number: PB0370000 UN/NA & ERG Number: UN1670 (inhalation zone B)/157 EC Number: 209-840-4 Regulatory Authority and Advisory Bodies Department of Homeland Security Screening Threshold Quantity (pounds): Release hazard 10,000 ($1.00% concentration). Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. OSHA 29CFR1910.119, Appendix A, Process Safety List of Highly Hazardous Chemicals, TQ 5 150 lb (67.5 kg). US DOT 49CFR172.101, Inhalation Hazardous Chemical. Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: not listed in Annex 1. WGK (German Aquatic Hazard Class): No value assigned. Description: Perchloromethyl mercaptan is a pale yellow oily liquid with a foul-smelling, unbearable, acrid odor. Molecular weight 5 185.87; Specific gravity (H2O:1) 5 1.69; Boiling point 5 (decomposes) 147.2 C; Vapor pressure 5 3 mmHg at 25 C. Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 0, Reactivity 0. Insoluble in water. Potential Exposure: Compound Description: Primary Irritant. Perchloromethyl mercaptan is used as an intermediate for the synthesis of dyes and fungicides, such as Captan and Folpet. It has been considered as a warfare tear gas because of its highly irritant properties. Incompatibilities: Water contact forms HCl, sulfur, and carbon dioxide. Reacts with alkalies, amines, hot water, alcohols, oxidizers, reducing agents, iron, and steel. Attacks most metals. Permissible Exposure Limits in Air Conversion factor: 1 ppm 5 7.60 mg/m3 at 25 C & 1 atm. OSHA PEL: 0.1 ppm/0.8 mg/m3 TWA. NIOSH REL: 0.1 ppm/0.8 mg/m3 TWA. ACGIH TLV®[1]: 0.1 ppm/0.76 mg/m3 TWA. NIOSH IDLH: 10 ppm. Protective Action Criteria (PAC)* TEEL-0: 0.013 ppm PAC-1: 0.013 ppm PAC-2: 0.3 ppm PAC-3: 0.9 ppm *AEGLs (Acute Emergency Guideline Levels) & ERPGs (Emergency Response Planning Guideline) are in bold face.
Perchloromethyl mercaptan Australia: TWA 0.1 ppm (0.8 mg/m3), 1993; Austria: MAK 0.1 ppm (0.8 mg/m3), 1999; Belgium: TWA 0.1 ppm (0.76 mg/m3), 1993; Denmark: TWA 0.1 ppm (0.8 mg/m3), 1999; Finland: STEL 0.1 ppm (0.8 mg/m3), 1999; France: VME 0.1 ppm (0.8 mg/m3), 1999; Norway: TWA 0.1 ppm (0.8 mg/m3), 1999; the Netherlands: MAC-TGG 0.8 mg/m3, 2003; Switzerland: MAK-W 0.1 ppm (0.8 mg/m3), KZG-W 0.2 ppm, 1999; Turkey: TWA 0.1 ppm (0.8 mg/m3), 1993; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: TWA 0.1 ppm. Several states have set guidelines or standards for PMM in ambient air[60] ranging from 8.0 μg/m3 (North Dakota) to 13.0 μg/m3 (Virginia) to 16.0 μg/m3 (Connecticut) to 19.0 μg/m3 (Nevada). Determination in Air: Sample collection by charcoal tube, analysis by gas liquid chromatography. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Irritates the eyes, skin, and respiratory tract. Higher exposures can cause pulmonary edema, a medical emergency that can be delayed for several hours. This can cause death. Signs and symptoms of acute exposure to perchloromethyl mercaptan may lead to liver, heart, and kidney damage. Respiratory effects include coughing, dyspnea (shortness of breath), painful breathing, and lung congestion. Tachycardia (rapid heart rate) is often observed. Nausea, vomiting, abdominal cramping, and diarrhea may also occur. Contact with Perchloromethyl mercaptan may result in severe dermatitis (red, inflamed skin), conjunctivitis (red, inflamed eyes), and burns with ulceration and severe pain. May cause death or permanent injury after short exposure to small quantities. Brief exposure to lower concentrations may produce central nervous system depression and lung, liver, and heart congestion. Severe exposures may be fatal. May be absorbed through the skin in quantities sufficient to cause general toxic effects. Ingestion may cause damage to mucous membranes and result in pain and burning of the mouth and throat, nausea, vomiting, cramps, and diarrhea. In severe cases, tissue ulceration and CNS depression may occur. Medical Surveillance: NIOSH lists the following tests: Blood Gas Analysis; chest X-ray, electrocardiogram, liver function tests; pulmonary function tests; pulmonary function tests: forced vital capacity, forced expiratory volume (1 s); sputum cytology; urinalysis (routine); white blood cell count/differential. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if
2087
heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Up to 1 ppm: CcrOv* (APF 5 10) [any chemical cartridge respirator with organic vapor cartridge(s)]; Sa* (APF 5 10) (any supplied-air respirator). Up to 2.5 ppm: Sa:Cf* (APF 5 25) (any supplied-air respirator operated in a continuous-flow mode); PaprOv* (APF 5 25) [any powered, air-purifying respirator with organic vapor cartridge(s)]. Up to 5 ppm: CcrFOv (APF 5 50) [any chemical cartridge respirator with a full face-piece and organic vapor cartridge(s)] or GmFOv (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or back-mounted organic vapor canister] or PaprTOv* (APF 5 50) [any powered, air-purifying respirator with a tight-fitting face-piece and organic vapor cartridge(s)]; or SaT: Cf* (APF 5 50) (any supplied-air respirator that has a tight-fitting face-piece and is operated in a continuous-flow mode); or SCBAF (APF 5 50) (any self-contained breathing apparatus with a full face-piece) or SaF (APF 5 50) (any supplied-air respirator with a full face-piece). Up to 10 ppm: SaF: Pd,Pp (APF 5 2000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd,Pp (APF 5 10,000) (any NIOSH/MSHA- or European Standard EN 149-approved self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positivepressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary, self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: GmFOv100 (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or back-mounted organic vapor canister having an N100, R100, or P100 filter] or SCBAE (any appropriate escape-type, self-contained breathing apparatus). *Substance reported to cause eye irritation or damage; may require eye protection. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this
2088
Perchloryl fluoride
chemical you should be trained on its proper handling and storage. Store in a cool, dry place. Protect from moisture, metals, oxidizing and reducing agents. Where possible, automatically pump liquid from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of 5 gallons or more of this chemical should be grounded and bonded. Drums must be equipped with selfclosing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: Perchloromethyl mercaptan requires a shipping label of “POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 6.1 and Packing Group I. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Ventilate area of spill or leak. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. It may be necessary to seek emergency assistance. Initial isolation and protective action distances Distances shown are likely to be affected during the first 30 min after materials are spilled and could increase with time. If more than one tank car, cargo tank, portable tank, or large cylinder involved in the incident is leaking, the protective action distance may need to be increased. You may need to seek emergency information from CHEMTREC at (800) 424-9300 or seek professional environmental engineering assistance from the US EPA Environmental Response Team at (908) 548-8730 (24-h response line). Small spills (From a small package or a small leak from a large package) First: Isolate in all directions (feet/meters) 100/30 Then: Protect persons downwind (miles/kilometers) Day 0.2/0.3 Night 0.2/0.3 Large spills (From a large package or from many small packages) First: Isolate in all directions (feet/meters) 300/100 Then: Protect persons downwind (miles/kilometers) Day 0.5/0.8 Night 0.9/1.5
Fire Extinguishing: This compound is neither flammable nor a serious fire hazard, although it will support combustion. Fight small fires with dry chemical, carbon dioxide, water spray, or foam, and large fires with water spray, fog, or foam. Move containers containing this compound away from fire area if possible. Fight fire from maximum distance. Dike fire control water for later disposal; do not scatter the material. Positive pressure breathing apparatus and special protective clothing should be worn. Poisonous gases, including chlorine and sulfur oxides, are produced in fire. Vapors are heavier than air and will collect in low areas. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Incineration together with a flammable solvent in a furnace equipped with afterburner and scrubber. References US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Perchloromethyl Mercaptan. Washington, DC: Chemical Emergency Preparedness Program New Jersey Department of Health and Senior Services. (February 2000). Hazardous Substances Fact Sheet: Perchloromethyl Mercaptan. Trenton, NJ
Perchloryl fluoride
P:0310
Molecular Formula: ClFO3 Common Formula: ClO3F Synonyms: Chlorine oxyfluoride; Chlorine fluoride oxide; Trioxychlorofluoride CAS Registry Number: 7616-94-6 RTECS® Number: SD1925000 UN/NA & ERG Number: UN3083/124 EC Number: 231-526-0 Regulatory Authority and Advisory Bodies Department of Homeland Security Screening Threshold Quantity (pounds): Theft hazard 45 ($25.67% concentration). Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section.
Perchloryl fluoride OSHA 29CFR1910.119, Appendix A. Process Safety List of Highly Hazardous Chemicals, TQ 5 5000 lb (2270 kg). US DOT 49CFR172.101, Inhalation Hazardous Chemical. Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: not listed in Annex 1. WGK (German Aquatic Hazard Class): No value assigned. Description: Perchloryl fluoride is a colorless gas with a characteristic sweet odor. Shipped as a liquefied compressed gas. Molecular weight 5 102.45; Boiling point 5 2 46.7 C; Freezing/Melting point 5 2 147.8 C; Relative vapor density (air 5 1) 5 3.64; Vapor pressure 5 10.5 atm at 25 C; Relative vapor density (air 5 1) 5 3.64. Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 2, Reactivity 3 (Oxidizer). Slightly soluble in water; solubility 5 0.06% at 20 C. Potential Exposure: Perchloryl fluoride has been used as a liquid oxidant in rocket propellant combinations, as an insulating gas in high-voltage electrical systems, as a fluorinating agent in organic synthesis. Incompatibilities: A strong oxidizer. Violent reaction with benzene, calcium hydride, combustibles, olefins, strong bases, sulfur, sulfuric acid, amines, reducing agents, alcohols. Contact with carbonaceous materials (such as charcoal) or finely divided metals (such as powdered magnesium, aluminum, zinc) are a fire and explosion hazard. Attacks some plastics, rubber, and coatings. Permissible Exposure Limits in Air Conversion factor: 1 ppm 5 4.19 mg/m3 at 25 C & 1 atm. OSHA PEL: 3 ppm/13.5 mg/m3 TWA. NIOSH REL: 3 ppm/14 mg/m3 TWA; 6 ppm/28 mg/m3 STEL. ACGIH TLV®[1]: 3 ppm/13 mg/m3 TWA; 6 ppm/25 mg/m3 STEL. NIOSH IDLH: 100 ppm. Protective Action Criteria (PAC)* TEEL-0: 1.5 ppm PAC-1: 1.5 ppm PAC-2: 4.0 ppm PAC-3: 12 ppm *AEGLs (Acute Emergency Guideline Levels) & ERPGs (Emergency Response Planning Guideline) are in bold face. Australia: TWA 3 ppm (14 mg/m3); STEL 6 ppm, 1993; Austria: MAK 2.5 mg[F]/m3, 1999; Belgium: TWA 3 ppm (13 mg/m3); STEL 6 ppm (25 mg/m3), 1993; Denmark: TWA 3 ppm (14 mg/m3), 1999; Finland: TWA 3 ppm (14 mg/m3); STEL 6 ppm (25 mg/m3), 1999; France: VME 3 ppm (14 mg/m3), 1999; Norway: TWA 3 ppm (14 mg/ m3), 1999; the Netherlands: MAC-TGG 14 mg/m3, 2003; Sweden: NGV 2 mg[F]/m3, 1999; Switzerland: MAK-W 3 ppm (13 mg/m3), 1999; United Kingdom: TWA 3 ppm (13 mg/m3); STEL 6 ppm (26 mg/m3), 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: STEL 6 ppm. Several states have set guidelines or standards for perchloryl fluoride in ambient air[60] ranging from 140280 μg/m3
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(North Dakota) to 230 μg/m3 (Virginia) to 270 μg/m3 (Connecticut) to 333 μg/m3 (Nevada). Determination in Air: Sample collection by impinger or fritted bubbler; analysis by ion-specific electrode. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Absorbed through the skin. Harmful Effects and Symptoms Short Term Exposure: Irritates the respiratory tract. May affect the blood, causing the destruction of red blood cells; formation of methemoglobin. Cyanosis and anemia may result. The liquid may cause frostbite. Long Term Exposure: May cause anemia. Repeated high exposures can cause deposits of fluorides in the bones (fluorosis), which may cause pain, disability, and mottling of the teeth. Repeated exposure may cause nausea, vomiting, loss of appetite, diarrhea, or constipation. Points of Attack: Respiratory system, skin, blood. Medical Surveillance: NIOSH lists the following tests: Blood Gas Analysis; whole blood (chemical/metabolite), Methemoglobin; Complete blood count; chest X-ray; pulmonary function tests: forced vital capacity, forced expiratory volume (1 s); sputum cytology; urine (chemical/ metabolite); white blood cell count/differential. Consider the points of attack in preplacement and periodic physical examinations. Fluoride level in urine (use NIOSH #8308). Levels higher than 4 mg/L may indicate overexposure. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. If frostbite has occurred, seek medical attention immediately; do NOT rub the affected areas or flush them with water. In order to prevent further tissue damage, do NOT attempt to remove frozen clothing from frostbitten areas. If frostbite has NOT occurred, immediately and thoroughly wash contaminated skin with soap and water. Personal Protective Methods: Wear appropriate personal protective clothing to prevent the skin from becoming frozen from contact with the evaporating liquid or from contact with vessels containing the liquid. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear eye protection to prevent any reasonable probability of eye contact. Employees should wash
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Perchloryl fluoride
immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Up to 30 ppm: Sa (APF 5 10) (any supplied-air respirator). Up to 75 ppm: Sa:Cf* (APF 5 25) (any supplied-air respirator operated in a continuous-flow mode). Up to 100 ppm: SCBAF (APF 5 50) (any selfcontained breathing apparatus with a full face-piece) or SaF (APF 5 50) (any supplied-air respirator with a full facepiece). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd,Pp (APF 5 10,000) (any self-contained breathing apparatus that has a full facepiece and is operated in a pressure-demand or other positivepressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary self-contained breathing apparatus operated in a pressure-demand or other positivepressure mode). Escape: GmFS100 (APF 5 50) [any airpurifying, full-face-piece respirator (gas mask) with a chinstyle, front- or back-mounted canister providing protection against the compound of concern and having an N100, R100, or P100 filter] or SCBAE (any appropriate escape-type, selfcontained breathing apparatus). *Substance reported to cause eye irritation or damage; may require eye protection. Storage: (1) Color Code—Yellow: Reactive Hazard; Store in a location separate from other materials, especially flammables and combustibles. (2) Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in a cool, well-ventilated area away from incompatible materials listed above. Procedures for the handling, use and storage of cylinders should be in compliance with OSHA 1910.101 and 1910.169, as with the recommendations of the Compressed Gas Association. See OSHA Standard 1910.104 and NFPA 43A Code for the Storage of Liquid and Solid Oxidizers for detailed handling and storage regulations. Shipping: Perchloryl fluoride requires a shipping label of “POISON GAS, OXIDIZER.” It falls in Hazard Class 2.3. It is a violation of transportation regulations to refill compressed gas cylinders without the express written permission of the owner. Spill Handling: If in a building, evacuate building and confine vapors by closing doors and shutting down HVAC systems. Restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Ventilate area of spill or leak to disperse the gas. Wear chemical protective suit with selfcontained breathing apparatus to combat spills. Stay upwind and use water spray to “knock down” vapor; contain runoff. Stop the flow of gas, if it can be done safely from a distance. If source is a cylinder and the leak cannot be stopped in place, remove the leaking cylinder to a safe place; and repair leak or allow cylinder to empty. Keep this chemical out of confined spaces, such as a sewer, because of the
possibility of explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Initial isolation and protective action distances Distances shown are likely to be affected during the first 30 min after materials are spilled and could increase with time. If more than one tank car, cargo tank, portable tank, or large cylinder involved in the incident is leaking, the protective action distance may need to be increased. You may need to seek emergency information from CHEMTREC at (800) 424-9300 or seek professional environmental engineering assistance from the US EPA Environmental Response Team at (908) 548-8730 (24-h response line). Small spills (From a small package or a small leak from a large package) First: Isolate in all directions (feet/meters) 100/30 Then: Protect persons downwind (miles/kilometers) Day 0.1/0.2 Night 0.4/0.6 Large spills (From a large package or from many small packages) First: Isolate in all directions (feet/meters) 1500/500 Then: Protect persons downwind (miles/kilometers) Day 2.0/3.2 Night 5.2/8.4 Fire Extinguishing: Nonflammable gas, but will support combustion and add to the intensity of an existing fire. Poisonous gases, including fluorine, fluorine oxides, chlorine, and chlorine oxides, are produced in fire. Vapors are heavier than air and will collect in low areas. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If cylinders are exposed to excessive heat from fire or flame contact, withdraw immediately to a secure location. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Incineration together with flammable solvent in furnace equipped with afterburner and scrubber. Reference New Jersey Department of Health and Senior Services. (November 2001). Hazardous Substances Fact Sheet: Perchloryl Fluoride. Trenton, NJ
Phenanthrene
Persulfates See “Potassium Persulfate” as good example of this class of compounds.
Phenanthrene
P:0320
Molecular Formula: C4H10 Synonyms: Coal tar pitch volatiles: Phenanthrene; Phenanthren (German); Phenantrin CAS Registry Number: 85-01-8 RTECS® Number: VB2600000 UN/NA & ERG Number: Not regulated. EC Number: 201-581-5 Regulatory Authority and Advisory Bodies Carcinogenicity: IARC: Animal Inadequate Evidence; Human No Adequate Data, not classifiable as carcinogenic to humans, Group 3, 1987; EPA: Not Classifiable as to human carcinogenicity. OSHA, 29CFR1910 Specifically Regulated Chemicals (CFR1910.1002) as coal tar pitch volatiles. Clean Water Act: Section 307 Toxic Pollutants, 40CFR401.15 (effluent limitations); 40CFR413.02, Total Toxic Organics, 40CFR423, Priority Pollutants, as polynuclear aromatic hydrocarbons (PAH). RCRA 40CFR258, Appendix 2. RCRA 40CFR268.48; 61FR15654, Universal Treatment Standards: Wastewater (mg/L), 0.059; Nonwastewater (mg/ kg), 3.4. RCRA, 40CFR264, Appendix 9, Ground Water Monitoring List, Suggested Testing Methods (PQL μg/L): 8100 (200); 8270 (10). Superfund/EPCRA 40CFR302.4, Appendix A, Reportable Quantity (RQ): 100 lb (45.4 kg). Canada, WHMIS, Ingredients Disclosure List Concentration: 1% as phenanthrene; 0.1% as coal tar pitch volatiles; DSL list. Mexico, Drinking Water, Criteria (Ecological): 0.02 mg/L; wastewater: organic toxic pollutant. European/International Regulations: Hazard Symbol: Xn, N; Risk phrases: R22; R40; R50/53; Safety phrases: S29; S36/37; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): No value assigned. Description: Phenanthrene is a white[2] crystalline substance with a weak aromatic odor. Polynuclear aromatic hydrocarbons (PAHs) are compounds containing multiple benzene rings and are also called polycyclic aromatic hydrocarbons. Molecular weight 5 178.22.[2] Molecular weight 5 178.24; Boiling point 5 340 C at 760 mmHg[2]; Freezing/Melting point 5 100 C[2]; Flash point 5 171 C. Hazard Identification (based on NFPA-704 M Rating System): Health 2, Flammability 0, Reactivity 0. Insoluble in water. Potential Exposure: Mutagen. Used for making dyes, other chemicals; explosives, pharmaceuticals; in biological research.
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Incompatibilities: Oxidizers. Permissible Exposure Limits in Air: No specific standards have been established for phenanthrene. OSHA PEL: 0.2 mg/m3 TWA [1910.1002] (benzene-soluble fraction). OSHA defines “coal tar pitch volatiles” in 29 CFR 1910.1002 as the fused polycyclic hydrocarbons that volatilize from the distillation residues of coal, petroleum (excluding asphalt), wood, and other organic matter. NIOSH REL: 0.1 mg/m3 (cyclohexane-extractable fraction). NIOSH considers coal tar products (i.e., coal tar, coal tar pitch, or creosote) to be potential occupational carcinogens. ACGIH TLV®[1]: 0.2 mg/m3 TWA (as benzene-soluble aerosol); Confirmed Human Carcinogen. NIOSH IDLH: 80 mg/m3. Protective Action Criteria (PAC) TEEL-0: 2 mg/m3 PAC-1: 6 mg/m3 PAC-2: 40 mg/m3 PAC-3: 500 mg/m3 DFG MAK: [skin]. Several states have set guidelines or standards for coal tar pitch volatiles in ambient air[60] ranging from zero (North Carolina) to 0.0161 μg/m3 (Kansas) to 0.48 μg/m3 (Pennsylvania) to 2.0 μg/m3 (Connecticut and Virginia) to 5.0 μg/m3 (Nevada). Determination in Air: Use NIOSH Analytical Method #5506 polynuclear aromatic hydrocarbons by HPLC; NIOSH Analytical Method #5515, Polynuclear aromatic hydrocarbons by GC; OSHA Analytical Method ID-58. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Skin contact can cause irritation. A skin photosensitizer, contaminated skin exposed to sunlight can develop rash, skin burns, and blisters. Irritates the eyes and respiratory tract. Long Term Exposure: May cause skin allergy. If allergy develops, very low future exposure can cause itching and skin rash. Points of Attack: Skin, respiratory system, bladder, liver, kidneys. Medical Surveillance: NIOSH lists: complete blood count; chest X-ray; pulmonary function tests: Forced Vital Capacity; Forced Expiratory Volume (1 s); photopatch testing; sputum cytology; urinalysis (routine); cytology, hematuria.[2] First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical
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Phenazopyridine & phenazo-pyridine hydrochloride
facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: NIOSH: At any detectable concentration over 0.1 mg/m3: SCBAF: Pd,Pp (APF 5 10,000) (any NIOSH/MSHA- or European Standard EN 149-approved self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary, self-contained breathing apparatus operated in a pressuredemand or other positive-pressure mode). Escape: GmFOv100 (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or backmounted organic vapor canister having an N100, R100, or P100 filter] or SCBAE (any appropriate escape-type, selfcontained breathing apparatus). Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, wellventilated area away from strong oxidizers. Where possible, automatically transfer material from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of this chemical should be grounded and bonded. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: Not regulated. However, the “Acridine” standard may be used for this chemical. The required label is “POISONOUS/TOXIC MATERIALS.” It would fall in Hazard Class 6.1 and Packing Group III. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially
contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible solid. Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Poisonous gases are produced in fire. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant ($100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. References US EPA. (April 1975). Identification of Organic Compounds in Effluents from Industrial Sources, EPA-560/ 3-75-002. Washington, DC New Jersey Department of Health and Senior Services. (August 1999). Hazardous Substances Fact Sheet: Phenanthrene. Trenton, NJ
Phenazopyridine & phenazo-pyridine hydrochloride P:0330 Molecular Formula: C11H12ClN5 Synonyms: AP; 2,6-Diamino-3-phenylazopyridine; Diridone; DPP; Gastracid; Gastrotest; Mallophene; NC150; Phenazodine; Phenylazo; 3-(Phenylazo)-2,6-pyridinediamine; Pirid; Pyrazofen; Pyridacil; Pyridium; Pyripyridium; Sedural; Uridinal; Urodine; W 1655 Hydrochloride: Azodine; Azodium; Azodyne; Azo gantrisin; Azo gastanol; Azo-mandelamine; Azomine; Azo-standard; Azo-stat; Azotrex; Baridium; Bisteril; Cystopyrin; Cystural; 2,6-Diamino-3-phenylazopyridine hydrochloride; 2,6-Diamino-3-(phenylazo)pyridine monohydrochloride; Di-azo; Diridone; Dolonil; Eucistin; Giracid; Mallofeen; Mallophene; NC150; NCI-C01672; Nefrecil; PAP; PDP; Phenazo; Phenazodine; Phenazopyridine hydrochloride; Phenazopyridinium chloride; β-Phenylazo-α,α0 -diaminopyridine hydrochloride; 3-Phenylazo-2,6-diaminopyridine hydrochloride; Phenylazodiaminopyridine hydrochloride;
Phenazopyridine & phenazo-pyridine hydrochloride Phenylazo-α,α0 -diaminopyridine monohydrochloride; 3(Phenylazo)-2,6-pyridinediamine, hydrochloride; Phenylazopyridine hydrochloride; Phenyl-idium; Phenylidium 200; Pirid; Piridacil; Pyrazodine; Pyrazofen; Pyredal; Pyridacil; Pyridenal; Pyridene; Pyridiate; Pyridium; Pyridivite; Pyripyridium; Pyrizin; Sedural; Suladyne; Sulodyne; Thiosulfil-A forte; Urazium; Uridinal; Uriplex; Urobiotic-250; Urodine; Urofeen; Uromide; Urophenyl; Uropyridin; Uropyrine; Utostan; Vestin; W 1655 CAS Registry Number: 94-78-0; 136-40-3 (hydrochloride) RTECS® Number: US7875000 (hydrochloride); US7700000 UN/NA & ERG Number: UN2811 (toxic solid, organic, n. o.s.)/154 EC Number: 202-363-2; 205-243-8 (hydrochloride) Regulatory Authority and Advisory Bodies Carcinogenicity: (hydrochloride) IARC: Animal Sufficient Evidence; Human Limited Evidence, possibly carcinogenic to humans, Group 2B, 1987; NCI: Carcinogenesis Studies (feed); clear evidence: mouse; (feed); clear evidence: rat; NTP: Reasonably anticipated to be a human carcinogen. California Proposition 65 Chemical: Cancer 1/1/88; 1/1/88 (hydrochloride). European/International Regulations: not listed in Annex 1. WGK (German Aquatic Hazard Class): No value assigned. Description: Phenazopyridine is a red crystalline compound. Molecular weight 5 213.27; 249.73 (hydrochloride); Freezing/Melting point 5 (fine base) 139 C; 233238 C (hydrochloride). Slightly soluble in water. Potential Exposure: Phenazopyridine hydrochloride has been used for 50 years as an analgesic drug either alone or in combination with other drugs to reduce pain associated with urinary tract infection. Also used as a local anesthetic. Exposure to phenazopyridine hydrochloride occurs during manufacture and formulation. Incompatibilities: None listed. Permissible Exposure Limits in Air No standards or TEEL available. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Can affect you if swallowed. Symptoms of exposure include diarrhea, nausea, or vomiting; dehydration, decreased urine volume. May affect the development of red blood cells, causing cyanosis and methemoglobinemia and changes in blood sodium levels. Long Term Exposure: May affect the kidneys. Phenazopyridine hydrochloride was tested in mice and rats by oral administration. In female mice, it significantly increased the incidence of hepatocellular adenomas and carcinomas. In male and female rats, it induced tumors of the colon and rectum. Symptoms of exposure include deeply stained vomitus and urine, methemoglobinemia, Heinz body anemia, hepatic enlargement, abnormal renal function. May cause mutations. Points of Attack: Blood, kidneys.
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Medical Surveillance: Complete blood count (CBC). Kidney function tests. First Aid: Skin Contact[52]: Flood all areas of body that have contacted the substance with water. Do not wait to remove contaminated clothing; do it under the water stream. Use soap to help assure removal. Isolate contaminated clothing when removed to prevent contact by others. Eye Contact: Remove any contact lenses at once. Flush eyes well with copious quantities of water or normal saline for at least 2030 min. Seek medical attention. Inhalation: Leave contaminated area immediately; breathe fresh air. Proper respiratory protection must be supplied to any rescuers. If coughing, difficult breathing, or any other symptoms develop, seek medical attention at once, even if symptoms develop many hours after exposure. Ingestion: If convulsions are not present, give a glass or two of water or milk to dilute the substance. Assure that the person’s airway is unobstructed and contact a hospital or poison center immediately for advice on whether or not to induce vomiting. Note to physician: Treat for methemoglobinemia. Spectrophotometry may be required for precise determination of levels of methemoglobin in urine. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/ clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in pressure-demand or other positive-pressure mode. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in a refrigerator or a cool, dry place. Protect from air and light. A regulated, marked area should be established where this chemical is handled, used, or stored in compliance with OSHA Standard 1910.1045. Shipping: Toxic solids, organic, n.o.s. requires a shipping label of “POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 6.1 and Packing Group III.
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Phenol
Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible solid. Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Poisonous gases are produced in fire, including hydrogen chloride and nitrogen oxides. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode.
Phenol
P:0340
Molecular Formula: C6H6O Common Formula: C6H5OH Synonyms: Acide carbolique (French); Benzene, hydroxy-; Benzenol; Carbolic acid; Carbolsaure (German); ENT 1814; Fenol (Spanish); Hydroxybenzene; Monohydroxybenzene; Monophenol; NCI-C50124; Oxybenzene; Phenic acid; Phenole (German); Phenyl alcohol; Phenyl hydrate; Phenyl hydroxide; Phenylic acid; Phenylic alcohol CAS Registry Number: 108-95-2 RTECS® Number: SJ3325000 UN/NA & ERG Number: UN1671 (solid)/153; UN2312/ 153 (molten); UN2821 (solution)/153 EC Number: 203-632-7 [Annex I Index No.: 604-001-00-2] Regulatory Authority and Advisory Bodies Carcinogenicity: NCI: Carcinogenesis Bioassay (oral); no evidence: mouse, rat; IARC: Animal Inadequate Evidence; Human Inadequate Evidence, not classifiable as carcinogenic to humans, Group 3, 1999; EPA: Available data are inadequate for an assessment of human carcinogenic potential; Not Classifiable as to human carcinogenicity. US EPA Gene-Tox Program, Negative: N. crassa— reversion.
US EPA, FIFRA, 1998 Status of Pesticides: Supported. Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Clean Air Act: Hazardous Air Pollutants (Title I, Part A, Section 112). Clean Water Act: Section 311 Hazardous Substances/RQ 40CFR117.3 (same as CERCLA, see below); 40CFR401.15 Section 307 Toxic Pollutants; 40CFR423, Appendix A, Priority Pollutants; Section 313 Water Priority Chemicals (57FR41331, 9/9/92). US EPA Hazardous Waste Number (RCRA No.): U188. RCRA, 40CFR261, Appendix 8 Hazardous Constituents. RCRA 40CFR268.48; 61FR15654, Universal Treatment Standards: Wastewater (mg/L), 0.039; Nonwastewater (mg/kg), 6.2. RCRA 40CFR264, Appendix 9; TSD Facilities Ground Water Monitoring List. Suggested test method(s) (PQL μg/L): 8040 (1); 8270 (10). Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 500/10,000 lb (227/4540 kg). Reportable Quantity (RQ): 1000 lb (454 kg). EPCRA Section 313 Form R de minimis concentration reporting level: 1.0%. Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: Hazard Symbol: T; Risk phrases: R23/24/25; R34; R48/21/22/23; R68; Safety phrases: S1/2; S24/25; S26; S28; S36/37/39; S45 (see Appendix 4). WGK (German Aquatic Hazard Class): 2—Hazard to waters. Description: Phenol is a colorless to light pink crystalline solid with a sweet, acrid odor. Phenol liquefies by mixing with about 8% water. The odor threshold in air is 0.04 ppm and in water is 7.9 ppm. Molecular weight 5 94.12; Boiling point 5 182 C; Freezing/Melting point 5 42.8 C; Relative vapor density (air 5 1) 5 1.00 at 20 C; Vapor pressure 5 0.4 mmHg at 25 C; Relative vapor density (air 5 1): 3.2; Flash point 5 79.4 C (cc); Autoignition temperature 5 715 C. Explosive limits: LEL 5 1.3%; UEL 5 8.6%. Hazard Identification (based on NFPA-704 M Rating System) (liquid, crystals): Health 4, Flammability 2, Reactivity 1 (Corrosive). Soluble in water; solubility 5 9% at 25 C. Potential Exposure: Compound Description: Agricultural Chemical; Tumorigen, Mutagen; Reproductive Effector; Human Data; Primary Irritant. Phenol is used as a pharmaceutical, in the production of fertilizer; coke, illuminating gas; lampblack, paints, paint removers; rubber, asbestos goods; wood preservatives; synthetic resins; textiles, drugs, pharmaceutical preparations; perfumes, bakelite, and other plastics (phenol formaldehyde resins); polymer intermediates (caprolactam, bisphenol-A, and adipic acid). Phenol also finds wide use as a disinfectant and veterinary drug. Incompatibilities: The aqueous solution is a weak acid. Violent reaction with strong oxidizers, calcium hypochlorite, aluminum chloride, acids. Reacts with metals.
Phenol Permissible Exposure Limits in Air Conversion factor: 1 ppm 5 3.85 mg/m3 at 25 C & 1 atm. OSHA PEL: 5 ppm/19 mg/m3 TWA [skin]. NIOSH REL: 5 ppm/19 mg/m3 TWA [skin]; 15.6 ppm/ 60 mg/m3/15 min Ceiling Concentration. ACGIH TLV®[1]: 5 ppm/19 mg/m3 TWA [skin], not classifiable as a human carcinogen; BEI: 250 mg[total phenol]/g creatinine in urine/end-of-shift. NIOSH IDLH: 250 ppm. Protective Action Criteria (PAC)* TEEL-0: 5 ppm PAC-1: 15 ppm PAC-2: 23 ppm PAC-3: 200 ppm *AEGLs (Acute Emergency Guideline Levels) & ERPGs (Emergency Response Planning Guideline) are in bold face. DFG MAK; [skin], Carcinogen Category: 3B. Arab Republic of Egypt: TWA 5 ppm (19 mg/m3), [skin], 1993; Australia: TWA 5 ppm (19 mg/m3), [skin], 1993; Austria: MAK 5 ppm (19 mg/m3), [skin], 1999; Belgium: TWA 5 ppm (19 mg/m3), [skin], 1993; Denmark: TWA 1 ppm (4 mg/m3), [skin], 1999; Finland: TWA 5 ppm (19 mg/m3); STEL 10 ppm (38 mg/m3), [skin], 1999; France: VME 5 ppm (19 mg/m3), [skin], 1999; the Netherlands: MAC-TGG 8 mg/m3, [skin], 2003; Japan: 5 ppm (19 mg/m3), [skin], 1999; Norway: TWA 1 ppm (4 mg/m3), 1999; the Philippines: TWA 5 ppm (10 mg/m3), [skin], 1993; Poland: MAC (TWA) 10 mg/m3; MAC (STEL) 20 mg/m3, 1999; Russia: TWA 5 ppm; STEL 0.3 mg/m3, [skin], 1993; Sweden: NGV 1 ppm (4 mg/m3), KTV 2 ppm (8 mg/m3), [skin], 1999; Switzerland: MAK-W 5 ppm (19 mg/m3), KZG-W 10 ppm (38 mg/m3), [skin], 1999; Thailand: TWA 5 ppm (19 mg/m3), 1993; Turkey: TWA 5 ppm (19 mg/m3), [skin], 1993; United Kingdom: TWA 5 ppm (20 mg/m3); STEL 10 ppm, [skin], 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: not classifiable as a human carcinogen. Russia[35, 43] has also set a MAC of 0.01 mg/m3 (10 μg/m3) for ambient air in residential areas both on a momentary and a daily average basis. Many states have set guidelines or standards for phenol in ambient air[60] ranging, for example, from 10.0 μg/m3 (New York) to 45.23 μg/m3 (Kansas) to 52.0 μg/m3 (Massachusetts) to 95.0 μg/m3 (Indiana) to 190 μg/m3 (Florida, North Dakota, South Carolina) to 315.0 μg/m3 (Virginia) to 380.0 μg/m3 (Connecticut, North Dakota, South Dakota) to 452.0 μg/m3 (Nevada) to 456.0 μg/m3 (Pennsylvania) to 95.0 μg/m3 (North Carolina). Determination in Air: Use NIOSH Analytical Method (IV) #2546, Cresols and Phenol, OSHA Analytical Method 32. Permissible Concentration in Water: To protect freshwater aquatic life: 10,200 μg/L, based on acute toxicity data and 2560 μg/L, based on chronic toxicity data. To protect saltwater aquatic life: 5800 μg/L, based on acute toxicity data. For the protection of human health from phenol ingested
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through water and through contaminated aquatic organisms, the concentration in water should not exceed 3500 μg/L. For the prevention of adverse effects due to the organoleptic properties of chlorinated phenols inadvertently formed during water purification processes, the phenol concentration in water should not exceed 300 μg/L.[6] The Czech Republic[35] set a MAC of 0.2 mg/L for surface water and a MAC of 0.05 mg/L for drinking water. The EEC set a MAC of 0.5 μg/L in drinking water. Mexico has set maximum permissible concentrations of 1.0 μg/L in receiving waters used for drinking water supply; 1.0 mg/L in receiving water for recreational use; 0.1 mg/L in estuaries; and 0.01 mg/L in coastal waters. Russia[35, 43] set a MAC of 0.001 mg/L in drinking water. States which have set guidelines for phenol in drinking water[61] include California at 1.0 μg/L and Kansas at 300 μg/L. Determination in Water: Methylene chloride extraction followed by gas chromatography with flame ionization or electron capture detection (EPA Method 604) or gas chromatography plus mass spectrometry (EPA Method 625). Octanolwater coefficient: Log Kow 5 1.46. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Absorbed through the skin. Harmful Effects and Symptoms Short Term Exposure: Phenol and its vapor are corrosive to the eyes, skin, and respiratory tract. Eye contact can cause severe and painful burns and permanent damage. Skin contact may cause severe and painful burns, which promptly become anesthetized (numb) to touch, but deep damage and local gangrene can result. Significant skin contact or inhalation can cause death within minutes. Ulceration may follow. Inhalation can cause pulmonary edema, a medical emergency that can be delayed for several hours. This can cause death. May affect the central nervous system, heart, liver, and kidneys, causing convulsions, coma, cardiac disorders, respiratory failure, collapse. Signs and symptoms of acute exposure to phenol may be severe, and range from tachycardia (rapid heart rate) and tachypnea (rapid respiratory rate) to hypotension (low blood pressure), weak pulse, cardiac failure, pulmonary edema, and respiratory arrest. Cardiac arrhythmias may be noted. Weakness, headache, dizziness, tinnitus (ringing in the ears), delirium, and shock are common. Seizures may often be followed by coma. Pallor, profuse sweating, dilated pupils, and a profound drop in body temperature may occur. Gastrointestinal effects may include nausea, abdominal pain, bloody vomitus, and bloody diarrhea. Renal insufficiency may lead to hematuria (bloody urine). Toxic hazard rating is very toxic: probable oral lethal dose (human) is 50500 mg/kg. Ingestion of 1 g has been lethal to humans. Lethal amounts may be absorbed through skin or inhaled. Industrial contact can cause chronic poisoning with kidney and liver damage. Long Term Exposure: Repeated or prolonged contact with skin may cause dermatitis. The substance may damage the liver and kidneys and have an effect on the pancreas and heart muscle. May affect the central nervous system and
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Phenol
cause nerve and/or brain damage. Phenol causes mutations and may cause reproductive damage in humans; and may be a cancer risk. Points of Attack: Eyes, skin, respiratory system, liver, kidneys. Medical Surveillance: NIOSH lists the following tests: liver function tests; urine (chemical/metabolite); urine (chemical/metabolite), last 2 h of 8-h exposure; urine (chemical/metabolite), end-of-shift; urine (chemical/metabolite), pre- and postshift; urinalysis. Urinary phenol (See also NIOSH #8305 Phenol and p-cresol in urine). These tests should be repeated if overexposure is suspected. Interview for brain effects. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. If concentrated phenol gets on a large area of the skin, immediately rush victim to shower and use at full blast; remove all contaminated clothing; scrub the contaminated area with soap for at least 10 min—water alone may be harmful. If polyethyleneglycol-300 is available, swab exposed area with cotton soaked in it. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Rinse mouth. Give plenty of water and/or vegetable oil to drink. Do not allow the consumption of alcohol. Induce vomiting. Do not make an unconscious person vomit. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. For phenol ,30%, sealed chemical materials with good to excellent resistance: polyethylene. For phenol .70%, sealed chemical materials with good to excellent resistance: butyl rubber; Neoprene™, Teflon™, Viton™, Silvershield™. Also, polyethylene offers limited protection. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: 50 ppm: CcrOv95 (APF 5 10) [any air-purifying half-mask respirator with organic vapor cartridge(s) in combination with an N95, R95, or P95 filter.
The following filters may also be used: N99, R99, P99, N100, R100, P100]; Sa (APF 5 10) (any supplied-air respirator). 125 ppm: Sa:Cf (APF 5 25) (any supplied-air respirator operated in a continuous-flow mode) or PaprOvHie (APF 5 25) (any air-purifying full-face-piece respirator equipped with an organic vapor cartridge in combination with a high-efficiency particulate filter). 250 ppm: CcrFOv100 (APF 5 50) [air-purifying full-face-piece respirator equipped with organic vapor cartridge(s) in combination with an N100, R100, or P100 filter] or GmFOv100 (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or back-mounted organic vapor canister having an N100, R100, or P100 filter] or PaprTOvHie (APF 5 50) [any powered, air-purifying respirator with a tight-fitting face-piece and organic vapor cartridge(s) in combination with a high-efficiency particulate filter] or SCBAF (APF 5 50) (any self-contained breathing apparatus with a full face-piece) or SaF (APF 5 50) (any supplied-air respirator with a full facepiece). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd,Pp (APF 5 10,000) (any self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary self-contained breathing apparatus operated in a pressuredemand or other positive-pressure mode). Escape: GmFOv100 (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or backmounted organic vapor canister having an N100, R100, or P100 filter] or SCBAE (any appropriate escape-type, selfcontained breathing apparatus). Storage: Color Code—White stripe: Contact Hazard; Store separately; not compatible with materials in solid white category. Prior to working with this chemical you should be trained on its proper handling and storage. Before entering confined space where this chemical may be present, check to make sure that an explosive concentration is not a danger. Phenol must be stored to avoid contact with calcium hypochlorite and other strong oxidizers (such as chlorine and bromine), since violent reactions occur. Store in tightly closed containers in a cool, well-ventilated area away from heat. Where possible, automatically pump liquid from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of 5 gallons or more of this chemical should be grounded and bonded. Drums must be equipped with self-closing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings.
Phenol, 3-(1-methylethyl)-, methylcarbamate Shipping: Molten phenol requires a shipping label of “POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 6.1 and Packing Group II. Solid phenol requires a shipping label of “POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 6.1 and Packing Group II. Phenol solutions require a shipping label of “POISONOUS/TOXIC MATERIALS.” They fall in DOT Hazard Class 6.1 and Packing Group II or III. Spill Handling: Remove all ignition sources. Spills must be disposed of immediately by properly protected personnel; no others should remain in area. Flush with flooding quantities of water, then use caustic soda solution for neutralization. Remove and isolate contaminated clothing at the site. Establish forced ventilation to keep levels below explosive limit. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Absorb liquids in vermiculite, dry sand, earth, or similar material and deposit in sealed containers for later disposal. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible solid or liquid. Flammable vapors are produced when phenol is heated. Small fires: dry chemical, carbon dioxide, water spray, or alcohol foam. Large fires: water spray, fog, or foam; use water spray to cool containers in fire area. Move container from fire area if it can be done without risk; fight fire from maximum distance. Dike fire control water for later disposal; do not scatter the material. Poisonous gases are produced in fire. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. Vapors are heavier than air and will collect in low areas. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant ($100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. Incineration.
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References National Institute for Occupational Safety and Health. (1976). Criteria for a Recommended Standard: Occupational Exposure to Phenol, NIOSH Document No. 76-196 US Environmental Protection Agency. (1980). Phenol: Ambient Water Quality Criteria. Washington, DC US Environmental Protection Agency. (April 30, 1980). Phenol: Health and Environmental Effects Profile No. 144. Washington, DC: Office of Solid Waste Sax, N. I. (Ed.). (1983). Dangerous Properties of Industrial Materials Report, 3, No. 4, 7784 US Public Health Service. (December 1988). Toxicological Profile for Phenol. Atlanta, GA: Agency for Toxic Substances and Disease Registry US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Phenol. Washington, DC: Chemical Emergency Preparedness Program New York State Department of Health. (April 1986). Chemical Fact Sheet: Phenol. Albany, NY: Bureau of Toxic Substance Assessment New Jersey Department of Health and Senior Services. (June 2001). Hazardous Substances Fact Sheet: Phenol. Trenton, NJ
Phenol, 3-(1-methylethyl)-, methylcarbamate
P:0350
Molecular Formula: C11H15NO2 Synonyms: Carbamic acid, methyl-, m-cumenyl ester; Compound 10854; m-Cumenol methylcarbamate; m-Cumenyl methylcarbamate; ENT 25,500; ENT25,543; H 5727; H 8757; Hercules AC5727; Hercules 5727; HIP; m-Isopropylphenol N-methylcarbamate; m-Isopropylphenol methylcarbamate; 3-Isopropylphenol N-methylcarbamate; 3-Isopropylphenol methylcarbamate; m-Isopropylphenyl N-methylcarbamate; 3-Isopropylphenyl methylcarbamate; Methylcarbamic acid m-cumenyl ester; 3-(1-Methylethyl) phenol methylcarbamate; N-Methyl-m-isopropylphenyl carbamate; N-Methyl-3-isopropylphenyl carbamate; OMS-15; m-Psopropylphenyl methylcarbamate; UC 10854; Union Carbide UC10,854 CAS Registry Number: 64-00-6 RTECS® Number: FB7875000 UN/NA & ERG Number: UN2757/151 EC Number: 200-572-3 Regulatory Authority and Advisory Bodies Reportable Quantity (RQ): 10 lb (4.54 kg). RCRA 40CFR268.48; 61FR15654, Universal Treatment Standards: Wastewater (mg/L), 0.056; Nonwastewater (mg/ kg), 1.4 as m-cumenyl methylcarbamate. Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 500/ 10,000 lb (227/4540 kg).
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Phenol, 3-(1-methylethyl)-, methylcarbamate
Reportable Quantity (RQ): 10 lb (4.54 kg). European/International Regulations: not listed in Annex 1. WGK (German Aquatic Hazard Class): No value assigned. Description: Phenol, 3-(1-methylethyl)-, methylcarbamate is a white, crystalline, odorless solid. Molecular weight 5 193.27; Freezing/Melting point 5 73 C. Soluble in water; 270 mg/L at 25 C. Potential Exposure: Used as a carbamate insecticide. Incompatibilities: Strong alkalies. Permissible Exposure Limits in Air Protective Action Criteria (PAC)* TEEL-0: 3 mg/m3 PAC-1: 10 mg/m3 PAC-2: 16 mg/m3 PAC-3: 16 mg/m3 Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Absorbed through the skin. Harmful Effects and Symptoms Short Term Exposure: Irritates the eyes and respiratory tract causing coughing, wheezing, shortness of breath. Inhalation or skin contact can cause rapid, severe carbamate poisoning with headache, dizziness, blurred vision, nervousness, weakness, nausea, cramps, diarrhea, and discomfort in the chest. Signs also include sweating, tearing, salivation, vomiting, cyanosis, convulsions, coma, loss of reflexes and loss of sphincter control, death. LD50 5 (oral-guinea pig) 10 mg/kg. Long Term Exposure: May affect the nervous system. Cholinesterase inhibitor; cumulative effect is possible. This chemical may damage the nervous system with repeated exposure, resulting in convulsions, respiratory failure. May cause liver damage. Points of Attack: Respiratory system, lungs, central nervous system, cardiovascular system, skin, eyes, plasma and red blood cell cholinesterase. Medical Surveillance: Before employment and at regular times after that, the following are recommended: plasma and red blood cell cholinesterase levels (tests for the enzyme poisoned by this chemical). If exposure stops, plasma levels return to normal in 12 weeks while red blood cell levels may be reduced for 13 months. When cholinesterase enzyme levels are reduced by 25% or more below preemployment levels, risk of poisoning is increased, even if results are in lower ranges of “normal.” Reassignment to work not involving organophosphate or carbamate pesticides is recommended until enzyme levels recover. If symptoms develop or overexposure occurs, repeat the above tests as soon as possible and get an examination of the nervous system. Also, consider complete blood count. Consider chest X-ray following acute overexposure. Do not drink any alcoholic beverages before or during use. Alcohol promotes absorption of organic phosphates. Refer to the NIOSH Criteria Documents #78-174 and #76-147 on manufacturing, formulating, and working safely with pesticides. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least
15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in pressure-demand or other positive-pressure mode. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, wellventilated area away from strong alkaline materials. Where possible, automatically transfer material from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of this chemical should be grounded and bonded. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: Carbamate pesticides, solid, toxic, require a shipping label of “POISONOUS/TOXIC MATERIALS.” Phenol, 3-(methylethyl)-, Methylcarbamate falls in Hazard Class 6.1 and Packing Group III. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical
Phenothiazine as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a noncombustible solid. Use extinguishing agents suitable for surrounding fire. Poisonous gases are produced in fire, including nitrogen oxides. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: In accordance with 40CFR165, follow recommendations for the disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by contacting your local or federal environmental control agency or by contacting your regional EPA office. Reference New Jersey Department of Health and Senior Services. (September 1999). Hazardous Substances Fact Sheet: Phenol, 3-(methylethyl)-, Methylcarbamate. Trenton, NJ
Phenothiazine
P:0360
Molecular Formula: C12H9NS Common Formula: S(C6H4)2NH Synonyms: AFI-tiazin; Agrazine; Antiverm; Biverm; Contaverm; Dibenzoparathiazine; Dibenzothiazine; Dibenzo-1,4-thiazine; ENT 38; Feeno; Fenoverm; Fentiazin; Helmetina; Lethelmin; Nemazene; Nemazine; Orimon; Padophene; Penthazine; Phenegic; Phenosan; Phenoverm; Phenovis; Phenoxur; Phenthiazine; Reconox; Souframine; Thiodiphenylamin (German); Vermitin; Wurm-thional; XL-50 CAS Registry Number: 92-84-2 RTECS®Number: SN5075000 EC Number: 202-196-5 Regulatory Authority and Advisory Bodies US EPA Gene-Tox Program, Positive: Cell transform.— SA7/SHE. US EPA, FIFRA 1998 Status of Pesticides: Canceled. Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section.
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WGK (German Aquatic Hazard Class): 1—Low hazard to waters. Description: Phenothiazine is a greenish-yellow to greenish-gray crystalline substance with a slight odor and taste. Molecular weight 5 199.28; Boiling point 5 (decomposes) 371 C; Freezing/Melting point 5 185 C (sublimes). Hazard Identification (based on NFPA-704 M Rating System): Health 2, Flammability 1, Reactivity 0. Insoluble in water. Potential Exposure: Compound Description: Agricultural Chemical; Drug, Mutagen; Reproductive Effector; Human Data; Primary Irritant. Phenothiazine is used as an insecticide; as a base for the manufacture of tranquilizers; as anthelmintic in medicine and veterinary medicine; it is used widely as an intermediate in pharmaceutical manufacture; polymerization inhibitor, antioxidant. Incompatibilities: Organosulfides are incompatible with strong acids and acid fumes; elevated temperatures; sulfur oxides and nitrogen oxides can be produced. Contact with strong reducing agents, azo and diazo compounds, halocarbons, isocyanates can generate heat and may form explosive hydrogen gas. Permissible Exposure Limits in Air OSHA PEL: None. NIOSH REL: 5 mg/m3 TWA [skin]. ACGIH: 5 mg/m3 TWA [skin]. No TEEL available. Australia: TWA 5 mg/m3, [skin], 1993; Belgium: TWA 5 mg/m3, [skin], 1993; Denmark: TWA 5 mg/m3, [skin], 1999; Finland: TWA 5 mg/m3; STEL 10 mg/m3, [skin], 1999; France: VME 5 mg/m3, [skin], 1999; Norway: TWA 5 mg/m3, 1999; the Philippines: TWA 5 mg/m3, [skin], 1993; the Netherlands: MAC-TGG 5 mg/m3, [skin], 2003; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: 5 mg/m3 [skin]. Several states have set guidelines or standards for Phenothiazine is ambient air[60] ranging from 50 μg/m3 (North Dakota) to 80 μg/m3 (Virginia) to 100 μg/m3 (Connecticut) to 119 μg/m3 (Nevada). Determination in Air: No NIOSH Analytical Method available. Determination in Water: Octanolwater coefficient: Log Kow 5 4.2. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Skin absorption. Harmful Effects and Symptoms Short Term Exposure: Phenothiazine can affect you when breathed in and by passing through your skin. Exposure can irritate the skin and eyes. Exposure can cause an inflammation in the eye (keratitis). This can also be made worse by sunlight (photosensitization) and cause a severe skin reaction with rash and color changes. Can cause a severe allergic liver reaction. High levels of exposure may affect the blood cells, causing hemolytic anemia and toxic liver degeneration. Exposure may affect the nervous system, causing muscle twitching and shaking. May affect heart rhythm, causing irregular heartbeat.
2100
Phenothiazine
Long Term Exposure: Repeated or prolonged contact with skin may cause dermatitis and allergy. Can cause kidney and liver damage. Repeated or prolonged contact may cause skin sensitization as well as skin photophobia (abnormal visual intolerance to light). There is limited evidence that this chemical may damage the developing fetus. Several related phenothiazine compounds have been associated with human teratogenic effects. Points of Attack: Skin, cardiovascular system, liver, kidneys, heart. Medical Surveillance: For those with frequent or potentially high exposure (half the TLV or greater, or significant skin contact), the following are recommended before beginning work and at regular times after that: examination of the nervous system and eyes. Liver function tests, especially bile salts. Complete blood count. Evaluation by a qualified allergist, including careful exposure history and special testing, may help diagnose skin allergy. EKG. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/ clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Where there is potential for exposures over 5 mg/m3, use a NIOSH/MSHA- or European Standard EN149-approved full face-piece respirator with a highefficiency particulate filter. Greater protection is provided by a powered air-purifying respirator. Where there is potential for high exposures, use a NIOSH/MSHA- or European Standard EN149-approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuous-flow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a
full face-piece operated in pressure-demand or other positive-pressure mode. Storage: Color Code—Green: General storage may be used. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, well-ventilated area away from strong acids (such as hydrochloric, sulfuric, and nitric) since toxic fumes can result. Shipping: Not regulated. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: Phenothiazine may burn, but does not readily ignite. Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Poisonous gases are produced in fire, including sulfur oxides and nitrogen oxides. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Dissolve in combustible solvent and spray into incinerator equipped with afterburner and scrubber. In accordance with 40CFR165, follow recommendations for the disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by contacting your local or federal environmental control agency or by contacting your regional EPA office. References New Jersey Department of Health and Senior Services. (May 2000). Hazardous Substances Fact Sheet: Phenothiazine. Trenton, NJ US Environmental Protection Agency, Special Review and Reregistration Division Office of Pesticide Programs. (1998). Agency Status of Pesticides in Registration, Reregistration, and Special Review (Rainbow Report). Washington, DC
Phenyl dichloroarsine (Agent PD, WMD)
Phenyl dichloroarsine (Agent PD, WMD)
P:0370
Molecular Formula: C6H5AsCl2 Synonyms: Arsine, dichlorophenyl-; Arsonous dichloride, phenyl-; Diclorofenilarsina (Spanish); Dichlorophenylarsine; PD (military designation); Phenylarsinedichloride; Phenylarsonous dichloride; Phenyl arsonous dichloride; Phenyldichloroarsine CAS Registry Number: 696-28-6 RTECS®Number: CH5425000 UN/NA & ERG Number: UN1556/152 EC Number: 211-791-9 Regulatory Authority and Advisory Bodies Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. US EPA Hazardous Waste Number (RCRA No.): P036. RCRA, 40CFR261, Appendix 8 Hazardous Constituents. Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 500 lb (227 kg). Reportable Quantity (RQ): 1 lb (0.454 kg). US DOT 49CFR172.101, Inhalation Hazardous Chemical. As arsenic compounds Clean Air Act: Hazardous Air Pollutants (Title I, Part A, Section 112) as arsenic compounds. Clean Water Act: Toxic Pollutant (Section 401.15) as arsenic and compounds. RCRA, 40CFR261, Appendix 8 Hazardous Constituents, waste number not listed. Reportable Quantity (RQ): 1 lb (0.454 kg). EPCRA (Section 313): Includes any unique chemical substance that contain arsenic as part of that chemical’s infrastructure; Form R de minimis concentration reporting level: organics 1.0%. US DOT Regulated Marine Pollutant (49CFR172.101, Appendix B). Canada: Priority Substance List & Restricted Substances/ Ocean Dumping FORBIDDEN (CEPA), National Pollutant Release Inventory (NPRI) (arsenic compounds). European/International Regulations: not listed in Annex 1. WGK (German Aquatic Hazard Class): No value assigned. Description: Phenyldichloroarsine is a colorless or light yellow liquid or gas. Odorless. Molecular weight 5 222.93; Boiling point 5 257 C; Freezing/Melting point 5 19 C; Flash point 5 16 C. Hazard Identification (based on NFPA704 M Rating System): Health 4, Flammability 2, Reactivity 2 . Reaction with water; insoluble. Potential Exposure: It is used in organic synthesis and as a solvent. PD has been used as a military tear gas, vesicant, and blister agent. Incompatibilities: Contact with water forms HCl. Heat produces fumes of arsenic and chlorine. Attacks some metals in the presence of moisture.
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Permissible Exposure Limits in Air Arsenic, organic compounds OSHA PEL: 0.5 mg[As]/m3 TWA. NIOSH REL: Not established. See NIOSH Pocket Guide, Appendix A. ACGIH TLV®[1]: 0.01 mg[As]/m3 TWA; Confirmed Human Carcinogen; BEI established. Phenyl dichloroarsine; dichlorophenylarsine Protective Action Criteria (PAC)* TEEL-0: 0.061 mg/m3 PAC-1: 0.061 mg/m3 PAC-2: 0.061 mg/m3 PAC-3: 0.18 mg/m3 AEGLs (Acute Emergency Guideline Levels) & ERPGs (Emergency Response Planning Guideline) are in bold face. As arsenic, organic compounds TEEL-0: 0.5 mg/m3 PAC-1: 1.5 mg/m3 PAC-2: 2.5 mg/m3 PAC-3: 350 mg/m3 NIOSH IDLH: 5 mg[As]/m3. Determination in Air: Filter; Acid; Hydride generation atomic absorption spectrometry; NIOSH Analytical Method (IV) #7900. See also #7300, Elements (arsenic). Permissible Concentration in Water: EPA[6] recommends a zero concentration of arsenic for human health reasons but has set a guideline of 50 μg/L[61] for drinking water. Determination in Water: When phenyldichloroarsine mixes with water it breaks down into hydrochloric acid and arsenicals. For arsenic: The atomic absorption graphite furnace technique is often used for the measurement of total arsenic in water. It has also been standardized by EPA. Total arsenic may be determined by digestion followed by silver diethyldithiocarbamate; an alternative is atomic absorption; another is inductively coupled plasma (ICP) optical emission spectrometry. See OSHA Analytical Method #ID-105 for arsenic. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Phenyldichloroarsine reacts with many enzymes which damages the body. Phenyldichloroarsine will blind you and blister your skin severely, and with enough it will kill. You will know that you have been exposed when you feel immediate pain and you begin to vomit violently. Contact may cause burns to skin and eyes. Strong irritant to eyes, skin, and tissue. Corrosive if swallowed. Poisonous; may be fatal if inhaled, swallowed, or absorbed through skin. Vomiting and blistering are among symptoms of exposure. The median lethal dosage is 2600 mg-min/m3. The mean incapacitating dosage is 16 mg-min/m3 as a vomiting agent and 1800 mg-min/m3 as a blistering agent. 633 mg-min/m3 produces eye injury. Long Term Exposure: In animals: kidney damage; muscle tremor, seizure; possible gastrointestinal tract; reproductive effects; possible liver damage.
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Phenyl dichloroarsine (Agent PD, WMD)
Points of Attack: Skin, respiratory system, kidneys, central nervous system, liver, gastrointestinal tract, reproductive system. Medical Surveillance: Kidney function tests. Lung function tests. Consider chest X-ray following acute overexposure. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Speed in removing material from skin is of extreme importance. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Keep victim quiet and maintain normal body temperature. Effects may be delayed; keep victim under observation. Note to physician: For severe poisoning BAL [British antilewisite, dimercaprol, dithiopropanol (C3H8OS2)] has been used to treat toxic symptoms of certain heavy metal poisoning—including arsenic. Although BAL is reported to have a large margin of safety, caution must be exercised, because toxic effects may be caused by excessive dosage. Most can be prevented by premedication with 1-ephedrine sulfate (CAS: 134-72-5). For milder poisoning penicillamine (not penicillin) has been used, both with mixed success. Side effects occur with such treatment and it is never a substitute for controlling exposure. It can only be done under strict medical care. Decontamination: This is very important, and you have to decontaminate as soon as you can. Extra minutes before decontamination might make a big difference. If you do not have the equipment and training do not enter the hot or the warm zone to rescue and decontaminate victims. If the victim cannot move, decontaminate without touching and without entering the hot or the warm zone. Use clean water from any source; if possible, use a hose (spray or fog to prevent injury to the victim) or other system so that you would not have to touch the victim; do not even wait for soap or for the victim to remove clothing, begin washing immediately. Immediately flush the eyes with water for at least 15 min. Use caution to avoid hypothermia in children and the elderly. Washstripwashevacuate upwind and uphill: The approach is to immediately wash with water, then have the victim (not the first responder) remove all the victim’s clothing, then wash again (with soap if available) and then move away from the hot zone in an upwind and uphill direction. Wash the victim with warm water and soap. Decontaminate with diluted household bleach (0.5%, or one part bleach to 200 parts water), but do not let any get in the victim’s eyes, open wounds, or mouth. Wash off the
diluted bleach solution after 15 min. Be sure you have decontaminated the victims as much as you can before they leave the area so that they do not spread the phenyldichloroarsine. Use the antidote “Anti-Lewisite.” See “First Aid” above. Use 5% solution of common bleach (sodium hypochlorite) or calcium hypochlorite solution (48 oz per 5 gallons of water) to decontaminate scissors used in clothing removal, clothes and other items. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in pressure-demand or other positive-pressure mode. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, wellventilated area away from oxidizers. Where possible, automatically pump liquid from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of 5 gallons or more of this chemical should be grounded and bonded. Drums must be equipped with selfclosing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: Arsenic compounds, liquid, n.o.s. requires a shipping label of “POISONOUS/TOXIC MATERIALS.” Phenyl dichloroarsine falls in DOT Hazard Class 6.1 and Packing Group I. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Ventilate area of spill or leak. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as
m-Phenylenediamine a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Initial isolation and protective action distances Distances shown are likely to be affected during the first 30 min after materials are spilled and could increase with time. If more than one tank car, cargo tank, portable tank, or large cylinder involved in the incident is leaking, the protective action distance may need to be increased. You may need to seek emergency information from CHEMTREC at (800) 424-9300 or seek professional environmental engineering assistance from the US EPA Environmental Response Team at (908) 548-8730 (24-h response line). PD, when used as a weapon Small spills (From a small package or a small leak from a large package) First: Isolate in all directions (feet/meters) 100/30 Then: Protect persons downwind (miles/kilometers) Day 0.1/0.2 Night 0.1/0.2 Large spills (From a large package or from many small packages) First: Isolate in all directions (feet/meters) 100/30 Then: Protect persons downwind (miles/kilometers) Day 0.1/0.2 Night 0.1/0.2 Fire Extinguishing: Phenyl dichloroarsine may burn but does not ignite readily. Burned phenyl dichloroarsine is safer and better than the unburned product. In case of fire, evacuate the area. If there is some reason that you have to put out the fire—for example, there are things you cannot let burn nearby—use unattended equipment. You can fight phenyl dichloroarsine fires with water streams, water fog; ordinary foam; universal foam; and, for confined fires, carbon dioxide. Remember that phenyl dichloroarsine breaks down in water, forming toxic hydrochloric acid and arsenic chemicals. Wear positive pressure breathing apparatus. Move container from fire area if you can do it without risk. Fight fire from maximum distance. Dike fire control water for later disposal; do not scatter the material. Poisonous gases, including arsenic and chlorine, are produced in fire. Water produces corrosive chlorine fumes. Vapors are heavier than air and will collect in low areas. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control
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agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant ($100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. In accordance with 40CFR165, follow recommendations for the disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by contacting your local or federal environmental control agency or by contacting your regional EPA office. References US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Phenyl Dichloroarsine. Washington, DC: Chemical Emergency Preparedness Program Schneider, A. L., (Ed.) (2007). CHRIS 1 CD-ROM Version 2.0, United States Coast Guard Chemical Hazard Response Information System (COMDTINST 16465.12C). Washington, DC: United States Coast Guard and the Department of Homeland Security
m-Phenylenediamine
P:0380
Molecular Formula: C6H8N2 Synonyms: AI3-52607; 3-Aminoaniline; m-Aminoaniline; meta-Aminoaniline; Aminoaniline, meta-; Apco 2330; meta-Benzenediamine; m-Benzenediamine; 1,3Benzenediamine; Benzene, 1,3-diamino-; C.I. 76025; C.I. Developer 11; Developer 11; Developer C; Developer H; Developer M; meta-Diaminobenzene; m-Diaminobenzene; 1,3-Diaminobenzene; Direct brown BR; Direct brown GG; 1,3-Fenilendiamina (Spanish); m-Fenilendiamina (Spanish); Metaphenylenediamine; 3-Phenylenediamine; m-Phenylenediamine; Phenylenediamine, metaCAS Registry Number: 108-45-2 RTECS®Number: SS7700000 UN/NA & ERG Number: UN1673/153 EC Number: 203-584-7 [Annex I Index No.: 612-147-00-3] (m-) Regulatory Authority and Advisory Bodies Carcinogenicity: IARC: Animal Inadequate Evidence; Human No Adequate Data, not classifiable as carcinogenic to humans, Group 3, 1987.
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m-Phenylenediamine
US EPA Gene-Tox Program, Positive: SHE—clonal assay; Histidine reversion—Ames test; Inconclusive: Rodent dominant lethal. EPCRA Section 313 Form R de minimis concentration reporting level: 1.0%. Canada, WHMIS, Ingredients Disclosure List Concentration 0.1%. European/International Regulations: Hazard Symbol: T, N; Risk phrases: R20/21; R25; R36; R40; R43; R50/53; R68; Safety phrases: S1/2; S28; S36/37; S45; S60; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): 2—Hazard to waters. Description: m-Phenylenediamine is a colorless to white crystalline substance that turns red upon exposure to air. Molecular weight 5 108.16; Boiling point 5 287 C; Freezing/Melting point 5 64.4 C; Flash point 5 187 C; Autoignition temperature 5 555 C. Hazard Identification (based on NFPA-704 M Rating System): Health 0, Flammability 1, Reactivity 0. Soluble in water. Potential Exposure: Compound Description: Tumorigen, Mutagen; Reproductive Effector; Primary Irritant. Used in making various dyes; as a curing agent for epoxy resin; rubber, textile fibers; urethanes, corrosion inhibitors; adhesives; in photographic and analytical procedures and processes. Incompatibilities: Reacts violently with strong oxidizers, strong acids, acid chlorides, acid anhydrides, chloroformates. Heat and light contribute to instability. Keep away from metals. Permissible Exposure Limits in Air ACGIH TLV®[1]: 0.1 mg/m3 TWA [skin]; not classifiable as a human carcinogen. Protective Action Criteria (PAC) TEEL-0: 0.1 mg/m3 PAC-1: 0.3 mg/m3 PAC-2: 10 mg/m3 PAC-3: 125 mg/m3 DFG MAK: [skin]; Carcinogen Category 3B. Austria [skin], Suspected: carcinogen, 1999; Denmark: TWA 0.1 mg/m3, 1999; Norway: TWA 0.1 mg/m3, 1999; Switzerland: MAK-W 0.1 mg/m3, [skin], 1999; the Netherlands: MAC-TGG 0.1 mg/m3, 2003; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: not classifiable as a human carcinogen. Determination in Air: Use OSHA Analytical Method 87. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Contact can irritate the eyes and skin. Irritates the respiratory tract, causing coughing, wheezing, and/or shortness of breath. May affect the blood, causing the formation of methemoglobin and cyanosis with blue coloration of the skin and lips, headache, fatigue, dizziness. High levels can cause troubled breathing, collapse, and death. The p-isomer is more toxic and a more severe
irritant than the m-isomers. LD50 5 (oral-rat) 7201600 mg/kg. Long Term Exposure: Repeated or prolonged contact may cause skin sensitization and allergy. If allergy develops, very low future exposure can cause itching and a skin rash. Repeated or prolonged inhalation exposure may cause asthma-like allergy. May cause kidney and liver impairment. Exposure may cause anemia. Points of Attack: Respiratory system, skin, lungs, liver, kidneys, blood. Medical Surveillance: Consider the points of attack in preplacement and periodic physical examinations. Complete blood count (CBC). Examination of the eyes and vision. Evaluation by a qualified allergist. Lung function tests. Blood methemoglobin levels. Liver and kidney function tests. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Note to physician: Treat for methemoglobinemia. Spectrophotometry may be required for precise determination of levels of methemoglobin in urine. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Where there is potential for exposure to this chemical of more than 0.1 mg/m3, use a NIOSH/ MSHA- or European Standard EN149-approved suppliedair respirator with a full face-piece operated in the positivepressure mode, or with a full face-piece, hood, or helmet in the continuous-flow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in pressuredemand or other positive-pressure mode. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and
o-Phenylenediamine storage. Store in tightly closed containers in a cool, wellventilated area away from strong oxidizers. Where possible, automatically transfer material from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of this chemical should be grounded and bonded. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: Phenylenediamines require a shipping label of “POISONOUS/TOXIC MATERIALS.” They fall in DOT Hazard Class 6.1 and Packing Group III. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible solid. Use dry chemical, carbon dioxide, water spray, alcohol foam or polymer foam extinguishers. Poisonous gases are produced in fire, including nitrogen oxides. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are selfcontained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positivepressure mode. Disposal Method Suggested: Controlled incineration whereby oxides of nitrogen are removed from the effluent gas by scrubber, catalytic or thermal device.[22] Reference New Jersey Department of Health and Senior Services. (August 1999). Hazardous Substances Fact Sheet: mPhenylenediamine. Trenton, NJ
o-Phenylenediamine
P:0390
Molecular Formula: C6H8N2 Synonyms: AI3-24343; 2-Aminoaniline; o-Benzenediamine; 1,2-Benzenediamine; C.I. 76010; C.I. Oxidation base 16;
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o-Diaminobenzene; 1,2-Diaminobenzene; 1,2-Fenilendiamina (Spanish); o-Fenilendiamina (Spanish); OPDA; Orthamine; o-Phenylenediamine; Phenylenediamine, ortho-; PODA CAS Registry Number: 95-54-5 RTECS®Number: SS7875000 UN/NA & ERG Number: UN1673/153 EC Number: 202-430-6 [Annex I Index No.: 612-145-00-2] (o-) Regulatory Authority and Advisory Bodies US EPA Gene-Tox Program, Negative: Rodent dominant lethal; N. crassa—aneuploidy. RCRA 40CFR268.48; 61FR15654, Universal Treatment Standards: Wastewater (mg/L), 0.056; Nonwastewater (mg/kg), 5.6. EPCRA Section 313 Form R de minimis concentration reporting level: 1.0%. California Proposition 65 Chemical: Cancer 5/15/98. European/International Regulations: Hazard Symbol: T, N; Risk phrases: R20/21; R25; R36; R40; R43; R50/53; R68; Safety phrases: S1/2; S28; S36/37; S45; S60; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): 3—Severe hazard to waters. Description: o-Phenylenediamine is a white to brownish crystalline substance that turns red upon exposure to air. Molecular weight 5 108.16; Boiling point 5 257 C; Freezing/Melting point 5 104 C; Flash point 5 156 C. Hazard Identification (based on NFPA-704 M Rating System): Health 2, Flammability 1, Reactivity 0. Slightly soluble in water. Potential Exposure: Used as an intermediate in the making of dyes; pesticides, pharmaceuticals, and rubber chemicals; in making fungicides and other chemicals; in photographic and analytical procedures and processes. Incompatibilities: Reacts violently with strong oxidizers, strong acids, acid chlorides, acid anhydrides, chloroformates. Heat and light contribute to instability. Keep away from metals. Permissible Exposure Limits in Air ACGIH TLV®[1]: 0.1 mg/m3 TWA [skin]; confirmed animal carcinogen with unknown relevance to humans. Protective Action Criteria (PAC) TEEL-0: 0.1 mg/m3 PAC-1: 0.3 mg/m3 PAC-2: 200 mg/m3 PAC-3: 500 mg/m3 DFG MAK: [skin] Danger of skin sensitization; Carcinogen Category 3B. Austria: carcinogen, 1999; Denmark: TWA 0.1 mg/m3, 1999; Norway: TWA 0.1 mg/m3, 1999; Switzerland: MAKW 0.1 mg/m3, [skin], carcinogen, 1999. Determination in Air: Use OSHA Analytical Method 87. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Contact can irritate the eyes and skin. Eye contact may cause permanent damage. Irritates
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o-Phenylenediamine
the respiratory tract, causing coughing, wheezing, and/or shortness of breath. May affect the blood, causing the formation of methemoglobin and cyanosis with blue coloration of the skin and lips. Can cause stomach ache, headache, fatigue, dizziness, shaking, and convulsions. The p-isomer is more toxic and a more severe irritant than the o-isomers. Long Term Exposure: Repeated or prolonged contact may cause skin sensitization and allergy. If allergy develops, very low future exposure can cause itching and a skin rash. Repeated or prolonged inhalation exposure may cause asthma-like allergy. May cause kidney and liver impairment. Exposure may cause anemia. Points of Attack: Respiratory system, skin, lungs, liver, kidneys, blood. Medical Surveillance: Consider the points of attack in preplacement and periodic physical examinations. Complete blood count (CBC). Examination of the eyes and vision. Evaluation by a qualified allergist. Lung function tests. Blood methemoglobin levels. Liver and kidney function tests. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Note to physician: Treat for methemoglobinemia. Spectrophotometry may be required for precise determination of levels of methemoglobin in urine. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Where there is potential for exposure to this chemical of more than 0.1 mg/m3, use a NIOSH/ MSHA- or European Standard EN149-approved suppliedair respirator with a full face-piece operated in the positivepressure mode, or with a full face-piece, hood, or helmet in the continuous-flow mode; or use a NIOSH/MSHA- or
European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in pressuredemand or other positive-pressure mode. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, wellventilated area away from strong oxidizers. Where possible, automatically transfer material from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of this chemical should be grounded and bonded. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: Phenylenediamines require a shipping label of “POISONOUS/TOXIC MATERIALS.” They fall in DOT Hazard Class 6.1 and Packing Group III. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible solid. Use dry chemical, carbon dioxide, water spray, alcohol foam or polymer foam extinguishers. Poisonous gases are produced in fire, including nitrogen oxides. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are selfcontained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positivepressure mode. Disposal Method Suggested: Controlled incineration whereby oxides of nitrogen are removed from the effluent gas by scrubber, catalytic or thermal device.[22] Reference New Jersey Department of Health and Senior Services. (August 1999). Hazardous Substances Fact Sheet: o-Phenylenediamine. Trenton, NJ
p-Phenylenediamine
p-Phenylenediamine
P:0400
Molecular Formula: C6H8N2 Common Formula: H2NC6H4NH2 Synonyms: 4-Aminoaniline; p-Aminoaniline; BASF Ursol D; p-Benzenediamine; 1,4-Benzenediamine; Benzofur D; C.I. 76060; C.I. Developer 13; C.I. Oxidation base 10; Developer PF; p-Diaminobenzene; 1,4-Diaminobenzene; 1,4-Diaminobenzol; Durafur black R; 1,4-Fenilendiamina (Spanish); p-Fenilendiamina (Spanish); Fouramine D; Fourrine 1; Fourrine D; Fur black 41867; Fur brown 41866; Furro D; Fur yellow; Futramine D; Nako H; Orsin; Pelagol D; Pelagol grey D; Peltol D; 1,4Phenylenediamine; Phenylene diamine, para-; PPD; Renal PF; Santoflex IC; Tertral D; Ursol D; Vulkanox 4020; Zoba black D Hydrochloride: 1,4-Aminoaniline dihydrochloride; 1,4-Benzenediamine dihydrochloride; 1,4-Phenylenediame dihydrochloride CAS Registry Number: 106-50-3; 624-18-0 (dihydrochloride) RTECS®Number: SS8050000 UN/NA & ERG Number: UN1673/153 EC Number: 203-404-7 [Annex I Index No.: 612-028-006]; 210-834-9 [Annex I Index No.: 612-029-00-1] (p-phenylenediamine dihydrochloride) Regulatory Authority and Advisory Bodies Carcinogenicity: IARC: Animal Inadequate Evidence; Human No Adequate Data, not classifiable as carcinogenic to humans, Group 3, 1978. US EPA Gene-Tox Program, Positive: Cell transform.— RLV F344 rat embryo; Positive: Cell transform.—SA7/ SHE; D. melanogaster sex-linked lethal; Negative: Carcinogenicity—mouse/rat; Rodent dominant lethal; Negative: N. crassa—aneuploidy; Sperm morphology— mouse; Inconclusive: Mammalian micronucleus. Banned or Severely Restricted (several countries) (UN).[13] Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Clean Air Act: Hazardous Air Pollutants (Title I, Part A, Section 112). RCRA 40CFR264, Appendix 9; TSD Facilities Ground Water Monitoring List. Suggested test method(s) (PQL μg/ L): 8270 (10). Reportable Quantity (RQ): 1 lb (0.454 kg). EPCRA Section 313 Form R de minimis concentration reporting level: 1.0%. Canada, WHMIS, Ingredients Disclosure List Concentration 0.1%. European/International Regulations (includes dihydrochloride): Hazard Symbol: T, N; Risk phrases: R23/24/25; R36; R43; R50/53; Safety phrases: S1/2; S28; S36/37; S45; S60; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): 3—Severe hazard to waters.
2107
Description: p-Phenylenediamines are white to slightly red crystalline solids. They have been described as gray “light brown” which may result from exposure to air. Molecular weight 5 108.16; Specific gravity (H2O:1) 5 1.1; Boiling point 5 267 C (sublimes); Freezing/Melting point 5 146 C; Vapor pressure 5 ,1 mmHg at 25 C; Flash point 5 156 C; Autoignition temperature 5 400 C. Explosive limits: LEL 5 1.5%; UEL—unknown. Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 1, Reactivity 0. Slightly soluble in water; solubility 5 4% at 25 C. Potential Exposure: Compound Description: Agricultural Chemical; Tumorigen, Mutagen, Human Data; Primary Irritant. Compound Description: Agricultural Chemical; Tumorigen, Mutagen, Human Data; Primary Irritant. pPhenylenediamine has been used in dyestuff manufacture, in hair dyes, in photographic developers, in synthetic fibers, in polyurethanes, and as a monomer and in the manufacture of improved tire cords. Also used as a gasoline additive and in making antioxidants. Incompatibilities: A strong reducing agent. Reacts violently with strong oxidizers, strong acids, acid chlorides, acid anhydrides, chloroformates, and strong bases. Incompatible with organic anhydrides, isocyanates, aldehydes. Heat and light contribute to instability. Keep away from metals. Permissible Exposure Limits in Air OSHA PEL: 0.1 mg/m3 TWA [skin]. NIOSH REL: 0.1 mg/m3 TWA [skin]. ACGIH TLV®[1]: 0.1 mg/m3 TWA; not classifiable as a human carcinogen. NIOSH IDLH: 25 mg/m3. Protective Action Criteria (PAC) TEEL-0: 0.1 mg/m3 PAC-1: 6 mg/m3 PAC-2: 25 mg/m3 PAC-3: 25 mg/m3 Dihydrochloride TEEL-0: 0.6 mg/m3 PAC-1: 1.5 mg/m3 PAC-2: 12.5 mg/m3 PAC-3: 60 mg/m3 DFG MAK: 0.1 mg/m3, measured as the inhalable fraction TWA; Peak Limitation Category II(2); [skin], danger of skin sensitization; Carcinogen Category 3; Pregnancy Risk Group C. Australia: TWA 0.1 mg/m3, [skin], 1993; Austria: MAK 0.1 mg/m3, [skin], Suspected: carcinogen, 1999; Belgium: TWA 0.1 mg/m3, [skin], 1993; Denmark: TWA 0.1 mg/m3, [skin], 1999; Finland: TWA 0.1 mg/m3; STEL 0.3 mg/m3, [skin], 1999; France: VME 0.1 mg/m3, [skin], 1999; the Netherlands: MAC-TGG 0.1 mg/m3, [skin], 2003; the Philippines: TWA 0.1 mg/m3, [skin], 1993; Poland: MAC (TWA) 0.1 mg/m3; MAC (STEL) 0.3 mg/m3, 1999; Russia: STEL 0.05 mg/m3, 1993; Sweden: NGV 0.1 mg/m3, KTV 0.3 mg/m3, [skin], 1999; United Kingdom: TWA 0.1 mg/m3, 2000; Argentina, Bulgaria, Columbia, Jordan,
2108
p-Phenylenediamine
South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: not classifiable as a human carcinogen. Several states have set guidelines or standards for p-phenylenediamine in ambient air[60] ranging from 0.33 μg/m3 (New York) to 1.0 μg/m3 (Florida, North Dakota, South Carolina) to 1.6 μg/m3 (Virginia) to 2.0 μg/m3 (Connecticut and Nevada). Determination in Air: Use OSHA Analytical Method 87. Permissible Concentration in Water: Russia[35, 43] set a MAC of 0.1 mg/L in surface water. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Absorbed through the skin. Harmful Effects and Symptoms Short Term Exposure: Contact can severely irritate and burn the eyes and skin. May cause permanent eye damage. Irritates the respiratory tract, causing coughing, wheezing, and/or shortness of breath. Inhalation of dust may irritate the pharynx and larynx; bronchial asthmatic reactions. Swelling of mouth and throat may be observed following ingestion. Exposure can cause abdominal pain, nausea, high blood pressure, dizziness, seizures, and even coma. May affect the blood, causing the formation of methemoglobin and cyanosis with blue coloration of the skin and lips, headache, fatigue, dizziness. High levels can cause troubled breathing, collapse, and death. The p-isomer is more toxic and a more severe irritant than the o- and m-isomers. Long Term Exposure: Repeated or prolonged contact may cause skin sensitization and allergy. If allergy develops, very low future exposure can cause itching and a skin rash. Repeated or prolonged inhalation exposure may cause asthma-like allergy. May cause kidney and liver impairment. Repeated high exposure can cause cataracts. Exposure may cause anemia. Points of Attack: Respiratory system, skin, lungs, liver, kidneys, blood. Medical Surveillance: Consider the points of attack in preplacement and periodic physical examinations. Complete blood count (CBC). Examination of the eyes and vision. Evaluation by a qualified allergist. Lung function tests. Blood methemoglobin levels. Liver and kidney function tests. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water or a slurry of activated charcoal in water; and induce vomiting. Do not make an unconscious person vomit. Note to physician: Treat for methemoglobinemia. Spectrophotometry may be required for precise determination of levels of methemoglobin in urine.
Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Up to 2.5 mg/m3: Sa:Cf (APF 5 25) (any supplied-air respirator operated in a continuous-flow mode). Up to 5 mg/m3: SCBAF (APF 5 50) (any selfcontained breathing apparatus with a full face-piece) or SaF (APF 5 50) (any supplied-air respirator with a full facepiece). Up to 25 mg/m3: SaF: Pd,Pp (APF 5 2000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd,Pp (APF 5 10,000) (any self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positivepressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: GmFS100 (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or back-mounted canister providing protection against the compound of concern and having an N100, R100, or P100 filter] or SCBAE (any appropriate escape-type, self-contained breathing apparatus). Note: Causes eye irritation and damage; eye protection needed. Storage: (1) Color Code—Yellow Stripe (strong reducing agent): Reactivity Hazard; Store separately in an area isolated from flammables, combustibles, or other yellow-coded materials. Prior to working with this chemical you should be trained on its proper handling and storage. Before entering confined space where this chemical may be present, check to make sure that an explosive concentration is not a danger. Store in tightly closed containers in a cool, wellventilated area away from oxidizers, strong acids, acid chlorides, acid anhydrides, chloroformates, and metals. Where possible, automatically transfer material from drums or other storage containers to process containers. Shipping: Phenylenediamines require a shipping label of “POISONOUS/TOXIC MATERIALS.” They fall in DOT Hazard Class 6.1 and Packing Group III. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in
Phenyl glycidyl ether sealed containers. Establish forced ventilation to keep levels below explosive limit. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible solid. Use dry chemical, carbon dioxide, water spray, alcohol foam or polymer foam extinguishers. Poisonous gases, including nitrogen oxides, are produced in fire. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Controlled incineration whereby oxides of nitrogen are removed from the effluent gas by scrubber, catalytic or thermal device.[22] References US Environmental Protection Agency. (June 1, 1978). Chemical Hazard Information Profile: Phenylenediamines. Washington, DC New Jersey Department of Health and Senior Services. (September, 1999). Hazardous Substances Fact Sheet: p-Phenylenediamine. Trenton, NJ
Phenyl glycidyl ether
P:0410
Molecular Formula: C9H10O2 Synonyms: 1,2-Epoxy-3-phenoxypropane; 2,3-Epoxypropylphenyl ether; Glycidyl phenyl ether; PGE; Phenol-glycidaether (German); Phenol glycidyl ether; 3-Phenoxy-1,2epoxypropane; Phenoxypropene oxide; Phenoxypropylene oxide; Phenyl-2,3-epoxypropyl ether CAS Registry Number: 122-60-1 RTECS®Number: TZ3675000 UN/NA & ERG Number: UN2810/153 EC Number: 204-557-2 [Annex I Index No.: 603-067-00-X] Regulatory Authority and Advisory Bodies Carcinogenicity: IARC: Animal Sufficient Evidence; Human No Adequate Data, possibly carcinogenic to humans, Group 2B, 1999; NIOSH: Potential occupational carcinogen.
2109
US EPA Gene-Tox Program, Positive: SHE—focus assay. Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. California Proposition 65 Chemical: Cancer 10/1/90; male 8/7/09. Canada, WHMIS, Ingredients Disclosure List Concentration 0.1%. European/International Regulations: Hazard Symbol: T, N; Risk phrases: R45; R20; R37/38; R43; R68; R52/53; Safety phrases: S53; S45; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): 3—Severe hazard to waters. Description: Phenyl glycidyl ether is a colorless liquid with an unpleasant sweet odor. Molecular weight 5 150.19; Specific gravity (H2O:1) 5 1.11; Boiling point 5 245 C; Freezing/Melting point 5 3.3 C; Vapor pressure 5 0.01 mmHg at 20 C; Flash point 5 120 C. Explosive limits: LEL 5 1.1%; UEL—unknown. Hazard Identification (based on NFPA-704 M Rating System): Health 2, Flammability 1, Reactivity 0. Slightly soluble in water; solubility 5 0.24% at 20 C. Potential Exposure: Compound Description: Tumorigen, Mutagen; Reproductive Effector; Primary Irritant. PGE is used to increase storage time and stability of halogenated compounds; as a reactive diluent in uncured epoxy resins to reduce the viscosity of the uncured system for ease in casting, adhesive, and laminating applications. NIOSH once estimated that 8000 workers are potentially exposed to PGE. Incompatibilities: Strong oxidizers, amines, strong acids, strong bases, and curing agents. PGE can presumably form explosive peroxides. Permissible Exposure Limits in Air Conversion factor: 1 ppm 5 6.14 mg/m3 at 25 C & 1 atm. OSHA PEL: 10 ppm/60 mg/m3 TWA. NIOSH REL: 1 ppm/6 mg/m3 [15 min] Ceiling Concentration; A potential occupational carcinogen [skin]; Limit exposure to lowest feasible concentration. See NIOSH Pocket Guide, Appendix A. ACGIH TLV®[1]: 0.1 ppm TWA [skin] danger of skin sensitization; confirmed animal carcinogen with unknown relevance to humans. No TEEL available. DFG MAK: [skin], danger of skin sensitization; Carcinogen Category 2. NIOSH IDLH: potential occupational carcinogen 100 ppm. Australia: TWA 1 ppm (6 mg/m3), 1993; Austria: [skin], carcinogen, 1999; Belgium: TWA 1 ppm (6.1 mg/m3), 1993; Denmark: TWA 1 ppm (5 mg/m3), 1999; Finland; STEL 10 ppm (60 mg/m3), [skin], 1999; France: VME 1 ppm (6 mg/m3), 1999; Norway: TWA 1 ppm (5 mg/m3), 1999; the Philippines: TWA 10 ppm (62 mg/m3), 1993; Poland: MAC (TWA) 0.6 mg/m3; MAC (STEL) 3 mg/m3, 1999; Sweden: NGV 10 ppm (60 mg/m3), KTV 15 ppm (90 mg/m3), 1999; Switzerland: MAK-W 1 ppm (6 mg/m3), [skin], carcinogen, 1999; Turkey: TWA 10 ppm (60 mg/m3), 1993; United
2110
Phenyl glycidyl ether
Kingdom: TWA 1 ppm (6.2 mg/m3), 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: confirmed animal carcinogen with unknown relevance to humans. Several states have set guidelines or standards for PGE in ambient air[60] ranging from 60 μg/m3 (Connecticut and North Dakota) to 100 μg/m3 (Virginia) to 143 μg/m3 (Nevada). Determination in Air: Use NIOSH Analytical Method (IV), Phenyl glycidyl ether. Determination in Water: Octanolwater coefficient: Log Kow 5 1.1. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: The substance irritates the eyes, skin, and upper respiratory tract. Eye and skin irritation may be severe. Exposure could cause lowering of consciousness, with headache, loss of concentration, dizziness, and unconsciousness. Long Term Exposure: Repeated or prolonged contact may cause skin sensitization and allergy. Possible hematopoietic, reproductive effects. A potential occupational carcinogen. Points of Attack: Eyes, skin, central nervous system, hematopoietic system, reproductive system. The liquid destroys the skin’s natural oils, causing dermatitis. Cancer site in animals: nasal cavity. Medical Surveillance: NIOSH lists the following tests: pulmonary function tests. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/ clothing material for your operation. Butyl rubber, natural rubber, and polyvinyl alcohol are among the recommended protective materials. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash.
Respirator Selection: At any detectable concentration: SCBAF: Pd,Pp (APF 5 10,000) (any NIOSH/MSHA- or European Standard EN 149-approved self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressuredemand or other positive-pressure mode in combination with an auxiliary, self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: GmFOv (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or back-mounted organic vapor canister] or SCBAE (any appropriate escapetype, self-contained breathing apparatus). Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Before entering confined space where this chemical may be present, check to make sure that an explosive concentration is not a danger. Store in a refrigerator or in a cool, dry place. Protect from exposure to acids, bases, oxidizers, and curing agents. Where possible, automatically pump liquid from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of 5 gallons or more of this chemical should be grounded and bonded. Drums must be equipped with self-closing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosionproof electrical equipment and fittings. A regulated, marked area should be established where this chemical is handled, used, or stored in compliance with OSHA Standard 1910.1045. Shipping: Toxic, liquids, organic, n.o.s. require a shipping label of “POISONOUS/TOXIC MATERIALS.” NNitrosodimethylamine falls in DOT Hazard Class 6.1 and Packing Group III. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Establish forced ventilation to keep levels below explosive limit. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Follow by washing surfaces well, first with 6070% ethanol; then with soap and with 6070% ethanol; then with soap and water. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific
Phenylhydrazine recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible liquid. Poisonous gases are produced in fire. Use dry chemical, carbon dioxide, or alcohol foam extinguishers. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Concentrated waste containing no peroxides—discharge liquid at a controlled rate near a pilot flame. Concentrated waste containing peroxides— perforation of a container of the waste from a safe distance followed by open burning. References US Environmental Protection Agency. (1979). Chemical Hazard Information Profile: Phenyl Glycidyl Ether. Washington, DC National Institute for Occupational Safety and Health. (1978). Criteria for a Recommended Standard: Occupational Exposure to Glycidyl Ethers, NIOSH Document No. 78-166. Washington, DC National Institute for Occupational Safety and Health. (October 1977). Information Profiles on Potential Occupational Hazards: Glycidyl Ethers, Report PB276,678. Rockville, MD, pp. 116123
Phenylhydrazine
P:0420
Molecular Formula: C6H8N2 Common Formula: C6H5NHNH2 Synonyms: Fenilhidrazina (Spanish); Hydrazine-benzene; Hydrazinobenzene; Monophenylhydrazine Hydrochloride: Cloruro de fenilhidrazinio (Spanish); Phenylhydrazine monohydrochloride; Phenylhydrazin hydrochlorid (German); Phenylhydrazinium chloride CAS Registry Number: 100-63-0; 59-88-1 (hydrochloride) RTECS® Number: MV8925000; MV9000000 (hydrochloride) UN/NA & ERG Number: UN2572/53
2111
EC Number: 202-873-5 [Annex I Index No.: 612-023-009]; 200-444-7 (phenylhydrazinium chloride) [Annex I Index No.: 612-023-00-9] Regulatory Authority and Advisory Bodies Carcinogenicity: NIOSH: Potential occupational carcinogen. Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. California Proposition 65 Chemical: (Phenylhydrazine and its salts) Cancer 7/1/92. Canada, WHMIS, Ingredients Disclosure List Concentration 0.1%. Hydrochloride: Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 1000/10,000 lb (454/4540 kg) (hydrochloride). Reportable Quantity (RQ): 1000 lb (454 kg) (hydrochloride). Canada, WHMIS, Ingredients Disclosure List Concentration 0.1%. European/International Regulations: Hazard Symbol (includes hydrochloride): T, N; Risk phrases: R45; R23/24/ 25; R36/38; R43; R48/23/24/25; R68; R50; Safety phrases: S53; S45; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): 3—Severe hazard to waters. Description: Phenylhydrazine is a colorless to pale yellow liquid or solid with a weak aromatic odor. The hydrochloride is a white to tan solid with a weak odor. Molecular weight 5 108.16; Specific gravity (H2O:1) 5 1.10 (base); Boiling point 5 (decomposes) 243.3 C (base); Freezing/ Melting point 5 19.4 C (base); 24 C (hemihydrate); 243246 C (hydrochloride); Vapor pressure 5 0.04 mmHg at 25 C; Flash point 5 88 C (cc) (base); Autoignition temperature 5 174 C (base). Explosive limits: LEL 5 1.1%; UEL—unknown. Hazard Identification (based on NFPA704 M Rating System): Health 3, Flammability 2, Reactivity 2; (hydrochloride) Hazard Identification (based on NFPA-704 M Rating System): Health 2, Flammability 0, Reactivity 0. Slightly soluble in water. Potential Exposure: Compound Description: Tumorigen, Mutagen; Reproductive Effector. Phenylhydrazine is a widely used reagent in conjunction with sugars, aldehydes, and ketones. In addition, it is used in the synthesis of dyes; pharmaceuticals, such as antipyrin, cryogenin, and pyramidone; and other organic chemicals. The hydrochloride salt is used in the treatment of polycythemia vera. Incompatibilities: Phenylhydrazine is very reactive with carbonyl compounds, strong oxidizers, strong bases, alkali metals, ammonia, lead dioxide (violent). Attacks copper salts, nickel, and chromates. Permissible Exposure Limits in Air Conversion factor: 1 ppm 5 4.42 mg/m3 at 25 C & 1 atm. OSHA PEL: 5 ppm/22 mg/m3 TWA [skin]. NIOSH REL: 0.14 ppm/0.6 mg/m3 [120 min] Ceiling Concentration [skin]; A potential occupational carcinogen
2112
Phenylhydrazine
[skin]; Limit exposure to lowest feasible concentration. See NIOSH Pocket Guide, Appendix A. ACGIH TLV®[1]: 0.1 ppm/0.44 mg/m3 TWA [skin]; confirmed animal carcinogen with unknown relevance to humans. NIOSH IDLH: 15 ppm (potential occupational carcinogen). Protective Action Criteria (PAC) Phenylhydrazine TEEL-0: 0.1 ppm PAC-1: 0.3 ppm PAC-2: 2 ppm PAC-3: 15 ppm Phenylhydrazine hydrochloride TEEL-0: 50 mg/m3 PAC-1: 150 mg/m3 PAC-2: 250 mg/m3 PAC-3: 250 mg/m3 DFG MAK: [skin], danger of skin sensitization; Carcinogen Category 3B. Arab Republic of Egypt: TWA 5 ppm (20 mg/m3), [skin], 1993; Australia: TWA 5 ppm (20 mg/m3); STEL 10 ppm, [skin], carcinogen, 1993; Austria: MAK 5 ppm (22 mg/m3), [skin], Suspected: carcinogen, 1999; Belgium: TWA 5 ppm (22 mg/m3); STEL 10 ppm, [skin], carcinogen, 1993; Denmark: TWA 0.1 ppm (0.6 mg/m3), [skin], 1999; Finland: STEL 5 ppm (22 mg/m3), [skin], 1999; Norway: TWA 0.6 mg/m3, 1999; the Philippines: TWA 5 ppm (22 mg/m3), 1993; Poland: MAC (TWA) 20 mg/m3, 1999; Switzerland: MAK-W 5 ppm (22 mg/m3), [skin], 1999; Turkey: TWA 5 ppm (22 mg/m3), [skin], 1993; United Kingdom: CHAN, 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: confirmed animal carcinogen with unknown relevance to humans. The Czech Republic[35]: MAC 1.0 mg/m3. Several states have set guidelines or standards for phenylhydrazine in ambient air[60] ranging from zero (North Dakota) to 66.7 μg/m3 (New York) to 200.0 μg/m3 (Connecticut, Florida, South Carolina, and Virginia) to 476.0 μg/m3 (Nevada). Determination in Air: Use NIOSH Analytical Method (IV) #3518. Permissible Concentration in Water: Russia[35, 43] set a MAC of 0.01 mg/L of phenylhydrazine in water bodies used for domestic purposes. Determination in Water: Octanolwater coefficient: Log Kow 5 1.25. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Absorbed through the skin. Harmful Effects and Symptoms Short Term Exposure: The dust and fumes can irritate and burn the eyes and skin. Inhalation can cause irritation, coughing, and difficult breathing. This material is poisonous if swallowed or if fumes are inhaled. Phenylhydrazine is a chronic poison. High levels can cause cyanosis and methemoglobinemia. Higher levels can cause troubled breathing, collapse, and even death. Exposure can cause headache,
nausea, vomiting, lightheadedness, nervousness, shaking, seizures, and coma. Long Term Exposure: Repeated or prolonged contact may cause skin irritation, dermatitis, sensitization, and allergy. May affect the blood, causing red cell damage, cyanosis, hemolytic anemia, kidney and liver damage, vascular thrombosis. A potential occupational carcinogen; it may cause leukemia. Points of Attack: Blood, respiratory system, liver, kidneys, skin. Cancer site in animals: lungs, liver, blood vessels, and intestine. May affect the bone marrow and cause leukemia. Medical Surveillance: NIOSH lists the following tests: blood plasma, hemoglobin; complete blood count; liver function tests; pulmonary function tests; urine (chemical/ metabolite), hemoglobin; urinalysis (routine); white blood cell count/differential. Evaluation by a qualified allergist. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Note to physician: Treat for methemoglobinemia. Spectrophotometry may be required for precise determination of levels of methemoglobin in urine. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash- or dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: At any detectable concentration: SCBAF: Pd,Pp (APF 5 10,000) (any NIOSH/MSHA- or European Standard EN 149-approved self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressuredemand or other positive-pressure mode in combination with an auxiliary, self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: SCBAE (any appropriate escape-type, selfcontained breathing apparatus).
Phenyl isocyanate Storage: (1) Color Code—Red Stripe (100-63-0): Flammability Hazard: Do not store in the same area as other flammable materials. (2) Color Code—Blue (hydrochloride, 59-88-1): Health Hazard: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in a refrigerator under an inert atmosphere and protect from exposure to light, strong bases, ammonia, oxidizers, metal salts. Where possible, automatically pump liquid from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of 5 gallons or more of this chemical should be grounded and bonded. Drums must be equipped with self-closing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. A regulated, marked area should be established where this chemical is handled, used, or stored in compliance with OSHA Standard 1910.1045. Shipping: Phenylhydrazine requires a shipping label of “POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 6.1 and Packing Group II. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Ventilate area of spill or leak. Avoid contact with solid and dust. Restrict access. Disperse and flush. Keep unnecessary people away; isolate hazard area and deny entry. Stay upwind; keep out of low areas. Do not touch spilled material; stop leak if you can do it without risk. Small liquid spills: take up with sand or other noncombustible absorbent material and place into containers for later disposal. Small dry spills: collect powdered material in the most convenient and safest manner and deposit in sealed containers; move container from spill area. Large spills: dike far ahead of spill for later disposal. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible liquid or solid, but does not easily ignite. Poisonous gases, including nitrogen oxides and hydrogen chloride, are produced in fire. Use dry chemical, carbon dioxide, alcohol foam, or polymer foam extinguishers. Vapors are heavier than air and will collect in low areas. Vapors in confined areas may explode when exposed to fire. Containers may explode in
2113
fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Controlled incineration whereby oxides of nitrogen are removed from the effluent gas by scrubber, catalytic or thermal device. References National Institute for Occupational Safety and Health. (1978). Criteria for a Recommended Standard: Occupational Exposure to Hydrazines, NIOSH Document No. 78-172. Washington, DC US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Phenylhydrazine Hydrochloride. Washington, DC: Chemical Emergency Preparedness Program New Jersey Department of Health and Senior Services. (September 1999). Hazardous Substances Fact Sheet: Phenylhydrazine Hydrochloride. Trenton, NJ
Phenyl isocyanate
P:0430
Molecular Formula: C7H5NO Common Formula: C6H5NCO Synonyms: Carbanil; Fenylisokyanat; Isocyanic acid, Phenyl ester; Karbanil; Mondur P; Phenylcarbimide; Phenyl carbonimide CAS Registry Number: 103-71-9 RTECS®Number: DA3675000 UN/NA & ERG Number: UN2487/155 EC Number: 203-137-6 Regulatory Authority and Advisory Bodies Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. US DOT 49CFR172.101, Inhalation Hazardous Chemical. European/International Regulations: Hazard Symbol: T; Risk phrases: R10; R22; R26; R34; R37; R42/43; Safety phrases: S/23; S/26; S28; S36/37/39; S38; S45; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): 2—Hazard to waters. Description: Phenyl isocyanate is a colorless liquid with an irritating odor. Molecular weight 5 119.30; Boiling point 5 160 C; Freezing/Melting point 5 30 C; Flash point 5 56 C. Hazard Identification (based on NFPA-704 M
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Phenyl isocyanate
Rating System): Health 1, Flammability 2, Reactivity 0. Decomposes in water. Potential Exposure: Compound Description: Mutagen. Phenyl isocyanate is used as a laboratory reagent and in organic synthesis. Incompatibilities: Forms explosive mixture with air. Violent reaction with strong oxidizers. Isocyanates are incompatible with acids, caustics, ammonia, amines, amides, alcohols, glycols, caprolactum solution, water. Permissible Exposure Limits in Air Protective Action Criteria (PAC)* TEEL-0: 0.006 mg/m3 PAC-1: 0.020 mg/m3 PAC-2: 0.15 mg/m3 PAC-3: 0.24 mg/m3 *AEGLs (Acute Emergency Guideline Levels) & ERPGs (Emergency Response Planning Guideline) are in bold face. DFG MAK: Danger of skin and airway sensitization. Russia[43] set a MAC of 0.5 mg/m3 in work-place air. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Absorbed through the skin. Harmful Effects and Symptoms Short Term Exposure: Phenyl isocyanate can affect you when breathed in and by passing through your skin. Exposure can strongly irritate the skin, nose, throat, and lungs. Higher levels may cause a buildup of fluid in the lungs (pulmonary edema). This can cause death. LD50 5 (oral-rat) 800 mg/kg. Long Term Exposure: Phenyl isocyanate can cause an asthma-like lung allergy to develop, with cough, shortness of breath, and wheezing. It can also cause an allergic skin rash. Points of Attack: Lungs, skin. Medical Surveillance: For those with frequent or potentially high exposure, the following are recommended before beginning work and at regular times after that: lung function tests. These may be normal if the person is not having an attack at the time of the test. If symptoms develop or overexposure is suspected, the following may be useful: evaluation by a qualified allergist, including careful exposure history and special testing, may help diagnose skin allergy. Consider chest X-ray after acute overexposure. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Medical observation is recommended for 2448 h after
breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Where there is potential for exposures to phenyl isocyanate, as a NIOSH/MSHA- or European Standard EN149-approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuous-flow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in pressure-demand or other positive-pressure mode. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, wellventilated area. Where possible, automatically pump liquid from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of 5 gallons or more of this chemical should be grounded and bonded. Drums must be equipped with self-closing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: Phenyl isocyanate requires a shipping label of “POISONOUS/TOXIC MATERIALS, FLAMMABLE LIQUID.” It falls in Hazard Class 6.1 and Packing Group I. A plus sign (1) indicates that the designated proper shipping name and hazard class of the material must always be shown whether or not the material or its mixtures or solutions meet the definitions of the class. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Ventilate area of spill or leak. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive
Phenyl mercaptan concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Initial isolation and protective action distances Distances shown are likely to be affected during the first 30 min after materials are spilled and could increase with time. If more than one tank car, cargo tank, portable tank, or large cylinder involved in the incident is leaking, the protective action distance may need to be increased. You may need to seek emergency information from CHEMTREC at (800) 424-9300 or seek professional environmental engineering assistance from the US EPA Environmental Response Team at (908) 548-8730 (24-h response line). Small spills (From a small package or a small leak from a large package) First: Isolate in all directions (feet/meters) 100/30 Then: Protect persons downwind (miles/kilometers) Day 0.3/0.5 Night 0.4/0.6 Large spills (From a large package or from many small packages) First: Isolate in all directions (feet/meters) 500/150 Then: Protect persons downwind (miles/kilometers) Day 1.0/1.5 Night 1.6/2.5 Fire Extinguishing: Phenyl isocyanate may burn, but does not readily ignite. Poisonous gases are produced in fire, including oxides of nitrogen. Containers may explode in fire. Use dry chemical, CO2, water spray; or foam extinguishers. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Reference New Jersey Department of Health and Senior Services. (November 2000). Hazardous Substances Fact Sheet: Phenyl Isocyanate. Trenton, NJ
Phenyl mercaptan
2115
P:0440
Molecular Formula: C6H6S Common Formula: C6H5SH Synonyms: Benzenethiol; Mercaptobenzene; Phenol, thio-; Phenylmercaptan; Phenylthiol; Thiophenol CAS Registry Number: 108-98-5 RTECS® Number: DC0525000 UN/NA & ERG Number: UN2337/131 EC Number: 203-635-3 Regulatory Authority and Advisory Bodies Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. US EPA Hazardous Waste Number (RCRA No.): P014. RCRA, 40CFR261, Appendix 8 Hazardous Constituents. Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 500 lb (227 kg). Reportable Quantity (RQ): 100 lb (45.4 kg). US DOT 49CFR172.101, Inhalation Hazardous Chemical. Canada, WHMIS, Ingredients Disclosure List Concentration 0.1%. European/International Regulations: not listed in Annex 1. WGK (German Aquatic Hazard Class): 3—Severe hazard to waters. Description: Phenyl mercaptan is a water-white liquid with a repulsive, penetrating, garlic-like odor. The odor threshold is 0.0003 ppm. Molecular weight 5 110.18; Specific gravity (H2O:1) 5 1.08; Boiling point 5 126 C; Freezing/Melting point 5 9.4 C; Vapor pressure 5 1 mmHg at 18 C; Flash point 5 55.6 C. Explosive limits: LEL 5 1.2%; UEL— unknown. Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 3, Reactivity 0. Insoluble in water. Potential Exposure: Compound Description: Reproductive Effector; Primary Irritant. Phenyl mercaptan is used as a chemical intermediate in pesticide manufacture; as a mosquito larvicide. It is used in solvent formulations for the removal of polysulfide sealants. Incompatibilities: Strong acids, strong bases, calcium hypochlorite, alkali metals. Oxidizes on exposure to air; supplied under nitrogen. At normal room temperature may vaporize forming explosive mixtures with air. Permissible Exposure Limits in Air OSHA PEL: None. NIOSH REL: 0.1 ppm/0.5 mg/m3 [15 min] Ceiling Concentration. ACGIH TLV®[1]: 0.1 ppm/0.45 mg/m3 TWA [skin]. Protective Action Criteria (PAC)* TEEL-0: 0.1 ppm PAC-1: 0.1 ppm PAC-2: 0.53 ppm PAC-3: 1.6 ppm *AEGLs (Acute Emergency Guideline Levels) & ERPGs (Emergency Response Planning Guideline) are in bold face.
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Phenyl mercaptan
Australia: TWA 0.5 ppm (2 mg/m3), 1993; Belgium: TWA 0.5 ppm (2.3 mg/m3), 1993; Denmark: TWA 0.5 ppm (2.3 mg/m3), 1999; Finland: STEL 0.5 ppm (2.6 mg/m3), 1993; France: VME 0.5 ppm (2 mg/m3), 1999; Norway: TWA 0.5 ppm (2 mg/m3), 1999; Switzerland: MAK-W 0.5 ppm (2.3 mg/m3), 1999; the Netherlands: MAC-TGG 2 mg/m3, 2003; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: TWA 0.5 ppm. Several states have set guidelines or standards for benzenethiol in ambient air[60] ranging from 20 μg/m3 (North Dakota) to 35 μg/m3 (Virginia) to 40 μg/m3 (Connecticut) to 48 μg/m3 (Nevada). Determination in Air: Use OSHA Analytical Method PV2075. Determination in Water: Octanolwater coefficient: Log Kow 5 2.52. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Absorbed through the skin. Harmful Effects and Symptoms Short Term Exposure: Benzenethiol can affect you when breathed in and by passing through your skin. Irritates the eyes, skin, and respiratory tract. Benzenethiol can severely burn the eyes, causing permanent damage. Higher exposures can cause pulmonary edema, a medical emergency that can be delayed for several hours. This can cause death. Exposure can cause weakness, dizziness, cough, wheezing, dyspnea (breathing difficulty). Higher levels can cause restlessness and irritability followed by paralysis and death. High or repeated exposure can cause liver, kidney, or lung damage. Acute exposure to thiophenol may result in cough, troubled breathing, irritation of the lungs, and pneumonitis. Nausea, vomiting, and diarrhea are often seen. May affect the nervous system. Long Term Exposure: Repeated or prolonged contact with skin may cause dermatitis. May cause lung, kidney, liver, spleen damage. Points of Attack: Eyes, skin, respiratory system, central nervous system, kidneys, liver, spleen. Medical Surveillance: If symptoms develop or overexposure is suspected, tests of the following may be helpful: Kidney and liver function. Lung function tests. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 30 min, occasionally lifting upper and lower lids. If available, flush eyes with large amounts of 0.5% silver nitrate, followed immediately by very large amounts of water. Continue water for 15 min. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Speed in removing material from skin is of extreme importance. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When
this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pneumonitis or pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: NIOSH: Up to 1 ppm: CcrOv (APF 5 10) [any chemical cartridge respirator with organic vapor cartridge(s)] or Sa (APF 5 10) (any supplied-air respirator). Up to 2.5 ppm: Sa:Cf (APF 5 25) (any supplied-air respirator operated in a continuous-flow mode) or PaprOv (APF 5 25) [any powered, air-purifying respirator with organic vapor cartridge(s)]. Up to 5 ppm: CcrFOv (APF 5 50) [any chemical cartridge respirator with a full face-piece and organic vapor cartridge(s)]; GmFOv (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or back-mounted organic vapor canister]; PaprTOv (APF 5 50) [any powered, air-purifying respirator with a tight-fitting face-piece and organic vapor cartridge(s)] or SCBAF (APF 5 50) (any self-contained breathing apparatus with a full face-piece) or SaF (APF 5 50) (any supplied-air respirator with a full face-piece). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd,Pp (APF 5 10,000) (any NIOSH/MSHA- or European Standard EN 149-approved self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary self-contained breathing apparatus operated in a pressuredemand or other positive-pressure mode). Escape: GmFOv (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or back-mounted organic vapor canister] or SCBAE (any appropriate escapetype, self-contained breathing apparatus). Storage: (1) Color Code—Red: Flammability Hazard: Store in a flammable liquid storage area or approved cabinet away from ignition sources and corrosive and reactive materials. (2) Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and
Phenylmercury acetate storage. Store in airtight containers in a cool, well-ventilated area. Sources of ignition, such as smoking and open flames, should be prohibited where benzenethiol is handled, used, or stored. Use only nonsparking tools and equipment, especially when opening and closing containers of benzenethiol. Shipping: This compound requires a shipping label of “POISONOUS/TOXIC MATERIALS, FLAMMABLE LIQUID.” It falls in Hazard Class 6.1 and Packing Group I. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Ventilate area of spill or leak. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Initial isolation and protective action distances Distances shown are likely to be affected during the first 30 min after materials are spilled and could increase with time. If more than one tank car, cargo tank, portable tank, or large cylinder involved in the incident is leaking, the protective action distance may need to be increased. You may need to seek emergency information from CHEMTREC at (800) 424-9300 or seek professional environmental engineering assistance from the US EPA Environmental Response Team at (908) 548-8730 (24-h response line). Small spills (From a small package or a small leak from a large package) First: Isolate in all directions (feet/meters) 100/30 Then: Protect persons downwind (miles/kilometers) Day 0.1/0.2 Night 0.1/0.2 Large spills (From a large package or from many small packages) First: Isolate in all directions (feet/meters) 100/30 Then: Protect persons downwind (miles/kilometers) Day 0.2/0.3 Night 0.3/0.5 Fire Extinguishing: This chemical is a flammable liquid. Poisonous gases, including sulfur dioxide, are produced in fire. Use dry chemical, carbon dioxide, or alcohol foam extinguishers. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or
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contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are selfcontained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positivepressure mode. Disposal Method Suggested: Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant ($100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. Dissolve in flammable solvent and burn in furnace equipped with afterburner and alkaline scrubber.[22] References US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Thiophenol. Washington, DC: Chemical Emergency Preparedness Program New Jersey Department of Health and Senior Services. (July 2004). Hazardous Substances Fact Sheet: Benzenethiol. Trenton, NJ
Phenylmercury acetate
P:0450
Molecular Formula: C8H8HgO2 Common Formula: C6H5HgOOCCH3 Synonyms: Acetate phenylmercurique (French); (Aceato) phenylmercury; Acetato fenilmercurio (Spanish); Acetic acid, phenylmercury derivitive; Agrosan; Agrosand; Agrosan GN 5; Algimycin; Antimucin WDR; Benzene, (acetoxymercuri)-; Benzene, (acetoxymercurio); Bufen; Cekusil; Celmer; Ceresan; Ceresan universal; Ceresol; Contra creme; Dynacide; Femma; FMA; Fungitox OR; Gallotox; HL-331; Hong kien; Hostaquick; Kwiksan; Leytosan; Liquiphene; Mercuriphenyl acetate; Mercury(II) acetate, phenyl; Mercury (acetoxy)phenyl-; Mergamma; Mersolite; Mersolite 8; Metasol 30; Norforms; Nymerate; Pamisan; Phenmad; Phenomercury acetate; Phenylmurcuriacetate; Phenylmercuric acetate; Phenylquecksilberacetat (German); Phix; PMA; PMAC; PM acetate; PMAL; PMAS; Purasan-SC-10; Puraturf 10; Quicksan; Sanitized SPG; SC-110; Scutl; Seedtox; Shimmerex; Sporkil; Tag; Tag 331; Tag HL 331; Tag fungicide; Trigosan; Ziarnik CAS Registry Number: 62-38-4; (alt.) 1337-06-0; (alt.) 61840-45-7; (alt.) 64684-45-3 RTECS® Number: OV6475000
2118
Phenylmercury acetate
UN/NA & ERG Number: UN1674/151 EC Number: 200-532-5 [Annex I Index No.: 080-011-00-5] Regulatory Authority and Advisory Bodies Carcinogenicity: IARC: Human Inadequate Evidence, possibly carcinogenic to humans, Group 2B, 1993. US EPA Gene-Tox Program, Positive: D. melanogaster— whole sex chrom. loss; Positive: D. melanogaster—nondisjunction; B. subtilis rec assay. US EPA, FIFRA 1998 Status of Pesticides: Canceled. Banned or Severely Restricted (several countries) (UN).[13] Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. US EPA Hazardous Waste Number (RCRA No.): P092. RCRA, 40CFR261, Appendix 8 Hazardous Constituents. Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 500/10,000 lb (227/4540 kg). Reportable Quantity (RQ): 100 lb (45.4 kg). US DOT Regulated Marine Pollutant (49CFR172.101, Appendix B), severe pollutant. California Proposition 65 Chemical: Reproductive toxin. Canada, WHMIS, Ingredients Disclosure List Concentration 0.1%. European/International Regulations: Hazard Symbol: T, N; Risk phrases: R25; R34; R48/24/25; R50/53; Safety phrases: S1/2; S3; S24/25; S37; S45; S60; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): 3—Severe hazard to waters. Description: Phenylmercury acetate is a white or yellow crystalline solid. Molecular weight 5 336.75; Freezing/Melting point 5 152 C; Flash point 5 .38 C. Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 1, Reactivity 0. Slightly soluble in water. Potential Exposure: Compound Description: Agricultural Chemical; Tumorigen, Organometallic, Mutagen; Reproductive Effector; Primary Irritant. Phenylmercury acetate is used as an antiseptic, fungicide; for fungal and bacterial control; herbicide and control of crabgrass; mildewcide for paints; slimicide in paper mills. It was also used in contraceptive gels and foams. Incompatibilities: Strong oxidizers, halogens. Permissible Exposure Limits in Air As organo mercury compound OSHA PEL: 0.01 mg/m3 TWA; 0.04 mg/m3 Ceiling Concentration. NIOSH REL: 0.01 mg/m3 TWA; 0.03 mg/m3 STEL [skin]. ACGIH TLV®[1]: 0.01 mg/m3 TWA; 0.03 mg/m3 STEL [skin]. NIOSH IDLH: 2 mg Hg/m3. Protective Action Criteria (PAC) TEEL-0: 0.168 mg/m3 PAC-1: 2.5 mg/m3 PAC-2: 16.8 mg/m3 PAC-3: 16.8 mg/m3 DFG MAK: 0.01 mg[Hg]/m3 [skin] Danger of skin sensitization; Carcinogen Category 3.
Australia: TWA 0.05 mg[Hg]/m3, [skin], 1993; Belgium: TWA 0.05 mg[Hg]/m3, [skin], 1993; Denmark: TWA 0.05 mg[Hg]/m3, [skin], 1999; Finland: TWA 1 mg[Hg]/ m3, 1999; France: VME 0.1 mg[Hg]/m3, [skin], 1999; Hungary: TWA 0.02 mg[Hg]/m3; STEL 0.04 mg[Hg]/m3, 1993; Japan: 0.05 mg[Hg]/m3, 1999; Norway: TWA 0.05 mg[Hg]/m3, 1999; the Philippines: TWA 0.05 mg [Hg]/m3, 1993; Poland: MAC (TWA) 0.05 mg[Hg]/m3; MAC (STEL) 0.15 mg[Hg]/m3, 1999; Russia: TWA 0.05 mg[Hg]/m3; STEL 0.01 mg[Hg]/m3, 1993; Sweden: NGV 0.05 mg[Hg]/m3, [skin], 1999; Thailand: STEL 0.05 mg[Hg]/m3, 1993; United Kingdom: LTEL 0.05 mg [Hg]/m3; STEL 0.15 mg[Hg]/m3, 1993; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: TWA 0.1 mg[Hg]/m3 [skin]. Permissible Concentration in Water: To protect freshwater aquatic life: 0.00057 μg/L as a 24-h average, never to exceed 0.0017 μg/L. To protect saltwater aquatic life: 0.025 μg/L as a 24-h average, never to exceed 3.7 μg/L. To protect human health: 0.144 μg/L (US EPA) set in 19791980.[6] These are the limits for inorganic mercury compounds in general. Determination in Water: Total mercury is determined by flameless atomic absorption. Soluble mercury may be determined by 0.45 μm filtration followed by flameless atomic absorption. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Absorbed through the skin. Harmful Effects and Symptoms Short Term Exposure: Irritates the eyes, skin, and respiratory tract. Overexposure affects the kidneys, causing renal function failure. Extremely toxic. The probable oral lethal dose for humans is 550 mg/kg, between 7 drops and 1 teaspoonful for a 70-kg (150 lb) person. Symptoms arising from acute exposure may occur at varying intervals up to several weeks following exposure. Ingestion of mercurial fungicide-treated grain resulted in gastrointestinal irritation with nausea, vomiting, abdominal pain, and diarrhea. Alkylmercurials produce severe neurologic toxicity, such as loss of feeling in lips, tongue, and extremities; confusion, hallucinations, irritability, sleep disturbances; staggering walk; memory loss; slurred speech; auditory defects; emotional instability; and inability to concentrate. It is also a strong skin irritant; erythema and blistering may result 612 h after exposure. Phenylmercury acetate, at sufficient concentration, is expected to be injurious to the eye externally. Mercury poisoning can cause “shakes,” irritability, sore gums; increased saliva; personality change and brain damage. Skin contact can cause burns, skin allergy, and a gray skin color. Heating or contact with acid or acid “fumes” releases toxic mercury vapors. Long Term Exposure: Mercury accumulates in the body. Repeated or prolonged contact with skin may cause dermatitis. May affect the nervous system, causing nervous disorders. Based on animal tests, phenylmercuric acetate should
Phenylmercury acetate be handled as a teratogen—with extreme caution. It also may cause mutations. Points of Attack: Eyes, skin, central nervous system, peripheral nervous system, kidneys. Medical Surveillance: Before first exposure and every 612 months after, a complete medical history and examination is strongly recommended with: examination of the nervous system, including handwriting. Routine urine test (UA). Urine test for mercury (should be less than 0.02 mg/ L). Consider lung function tests for persons with frequent exposures. After suspected illness or overexposure, repeat the above tests and get a blood test for mercury. Consider chest X-ray after acute overexposure. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Keep victim quiet and maintain normal body temperature. Effects may be delayed; keep victim under observation. Antidotes and Special Procedures for medical personnel: The drug NAP (n-acetyl penicillamine) has been used to treat mercury poisoning, with mixed success. Note to physician: For severe poisoning BAL [British AntiLewisite, dimercaprol, dithiopropanol (C3H8OS2)] has been used to treat toxic symptoms of certain heavy metal poisoning—including mercury. Although BAL is reported to have a large margin of safety, caution must be exercised, because toxic effects may be caused by excessive dosage. Most can be prevented by premedication with 1-ephedrine sulfate (CAS: 134-72-5). Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Specific engineering controls are recommended in NIOSH Criteria Document #73-11024. Respirator Selection: Up to 0.1 mg/m3: Sa (APF 5 10) (any supplied-air respirator). Up to 0.25 mg/m3: Sa:Cf (APF 5 25) (any supplied-air respirator operated in a
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continuous-flow mode). Up to 0.5 mg/m3: SaT: Cf (APF 5 50) (any supplied-air respirator that has a tight-fitting face-piece and is operated in a continuous-flow mode) or SCBAF (APF 5 50) (any self-contained breathing apparatus with a full face-piece) or SaF (APF 5 50) (any supplied-air respirator with a full face-piece). Up to 2 mg/m3: SA: PD, PP (any supplied-air respirator operated in a pressure-demand or other positive-pressure mode). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd,Pp (APF 5 10,000) (any NIOSH/ MSHA- or European Standard EN 149-approved selfcontained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary self-contained breathing apparatus operated in a pressure-demand or other positivepressure mode). Escape: SCBAE (any appropriate escapetype, self-contained breathing apparatus). Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, wellventilated area away from strong oxidizers (such as chlorine, bromine, and fluorine). Sources of ignition, such as smoking and open flames, are prohibited where phenylmercuric acetate is used, handled, or stored in a manner that could create a potential fire or explosion hazard. Shipping: Phenylmercuric acetate requires a shipping label of “POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 6.1 and Packing Group II. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Spills should be collected with special mercury vapor suppressants or special vacuums. Kits specific for cleanup of mercury spills should be available. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: Use dry chemical, foam, or carbon dioxide on solution. Use water as necessary, but run-off should be limited and controlled to prevent it from entering streams of water supplies. Materials are extremely hazardous to health, but areas may be entered with extreme care. Full protective clothing, including self-contained breathing apparatus; rubber gloves; boots and bands around legs, arms, and waist, should be provided. No skin should be exposed. Poisonous gases are produced in fire, including mercury. If material or contaminated runoff enters
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N-Phenyl-β-naphthylamine
waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant ($100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. React to produce soluble nitrate form, precipitate as mercuric sulfide. Return to supplier. References US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Phenylmercury Acetate. Washington, DC: Chemical Emergency Preparedness Program New Jersey Department of Health and Senior Services. (February 2000). Hazardous Substances Fact Sheet: Phenylmercuric Acetate. Trenton, NJ
N-Phenyl-β-naphthylamine
P:0460
Molecular Formula: C16H13N Common Formula: C10H7NHC6H5 Synonyms: 2-Anilinonaphthalene; β-Naphthylphenylamine; PBNA; 2-Phenylaminonaphthalene; Phenylβ-naphthylamine CAS Registry Number: 135-88-6 RTECS®Number: QV4550000 UN/NA & ERG Number: UN2811 (toxic solid, organic, n.o.s.)/154 EC Number: 205-223-9 [Annex I Index No.: 612-135-00-8] Regulatory Authority and Advisory Bodies Carcinogenicity: IARC: Animal Limited Evidence; Human Inadequate Evidence, not classifiable as carcinogenic to humans, Group 3, 1978; NCI: Carcinogenesis Studies (feed); equivocal evidence: mouse; no evidence: rat; NIOSH) (since metabolized to β-naphthylamine): Potential occupational carcinogen. Banned or Severely Restricted (Sweden) (UN).[13] Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Canada, WHMIS, Ingredients Disclosure List Concentration 0.1%. European/International Regulations: Hazard Symbol: Xn, N; Risk phrases: R36/38; R40; R43; R51/53; Safety phrases: S2; S26; S36/37; S61 (see Appendix 4).
WGK (German Aquatic Hazard Class): No value assigned. Description: Phenyl-β-naphthylamine is a light gray powder. A combustible solid. Molecular weight 5 219.30; Specific gravity (H2O:1) 5 1.24; Boiling point 5 396 C; Freezing/Melting point 5 107.8 C. Insoluble in water. Potential Exposure: Compound Description: Tumorigen, Mutagen. Phenyl-β-naphthylamine is used as a rubber antioxidant, as an inhibitor for butadiene, a stabilizer in lubricants, and an intermediate in chemical synthesis. Incompatibilities: Incompatible with oxidizers, strong acids, organic anhydrides, isocyanates, aldehydes. Permissible Exposure Limits in Air OSHA PEL: None. NIOSH REL: A potential occupational carcinogen* [skin]; Limit exposure to lowest feasible concentration. See NIOSH Pocket Guide, Appendix A. [*Note: Since metabolized to β-naphthylamine]. ACGIH TLV®[1]: not classifiable as a human carcinogen. No TEEL available. DFG MAK: Carcinogen Category 3B. Australia: carcinogen, 1993; Austria: Suspected: carcinogen, 1999; Belgium: carcinogen, 1993; Finland: carcinogen, 1999; Poland: MAC (TWA) 0.03 mg/m3, 1999; Sweden: carcinogen, 1999; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: not classifiable as a human carcinogen. Several states have set guidelines or standards for this compound in ambient air[60] ranging from zero (North Dakota) to 3.0 μg/m3 (Virginia) to 45.0 μg/m3 (Pennsylvania). Determination in Air: Use OSHA Analytical Method 96. Determination in Water: Octanolwater coefficient: Log Kow 5 4.4. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: The main problem with this compound is that phenyl-β-naphthylamine, a known carcinogen, is both a contaminant in, and a metabolic product of PBNA. Phenyl-β-naphthylamine can affect you when breathed in and by passing through your skin. Contact can cause skin irritation and rash. Phenyl-β-naphthylamine should be handled as a carcinogen—with extreme caution. Exposure can affect the ability of the blood to carry oxygen (methemoglobinemia), causing cyanosis, a bluish skin color. Higher levels can cause headache and dizziness. Very high levels can cause death. LD50 5 (oral-mouse) 1450 kg/mg. Long Term Exposure: Repeated or prolonged contact may cause skin irritation, sensitization, allergy; hypersensitivity to sunlight. A potential occupational carcinogen. Can cause methemoglobinemia (see above); anemia may result. Points of Attack: Eyes, skin, bladder. Cancer site: bladder; in animals: lung, pancreas. Medical Surveillance: If symptoms develop or overexposure is suspected, the following may be useful: methemoglobin level. Complete blood count (CBC).
o-Phenylphenol First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Note to physician: Treat for methemoglobinemia. Spectrophotometry may be required for precise determination of levels of methemoglobin in urine. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: At any detectable concentration: SCBAF: Pd,Pp (APF 5 10,000) (any NIOSH/MSHA- or European Standard EN 149-approved self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressuredemand or other positive-pressure mode in combination with an auxiliary, self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: GmFOv100 (APF 5 50) [any air-purifying, fullface-piece respirator (gas mask) with a chin-style, front- or back-mounted organic vapor canister having an N100, R100, or P100 filter] or SCBAE (any appropriate escapetype, self-contained breathing apparatus). Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, wellventilated area away from heat and oil. A regulated, marked area should be established where N-phenyl-β-naphthylamine is handled, used, or stored. Shipping: Toxic solids, organic, n.o.s. requires a shipping label of “POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 6.1 and Packing Group III. As a hazardous substance, solid, n.o.s., this imposes no label requirements or maximum on shipping weights.
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Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible solid. Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Poisonous gases are produced in fire, including nitrogen oxides. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. References National Institute for Occupational Safety and Health. (December 17, 1976). Metabolic Precursors of a Known Human Carcinogen, β-Naphthylamine, Current Intelligence Bulletin No. 16. Rockville, MD New Jersey Department of Health and Senior Services. (January 2007). Hazardous Substances Fact Sheet: NPhenyl-beta-Naphthylamine. Trenton, NJ
o-Phenylphenol
P:0470
Molecular Formula: C12H10O Common Formula: C6H5aC6H4OH Synonyms: Anthrapole 73; 2-Biphenylol; o-Biphenylol; (1,10 -Biphenyl)-2-ol; o-Biphenylol; o-Diphenylol; Dowicide 1; Dowcide 1 antimicrobial; o-Fenilfenol (Spanish); 2Hydroxybiphenyl; o-Hydroxybiphenyl; 2-Hydroxy-1,10 biphenyl; o-Hydroxydiphenyl; 2-Hydroxydiphenyl; Invalon OP; Kiwiydiphenyl; Nectryl; Orthophenylphenol; Orthoxenol; o-Phenylphenol; 2-Phenylphenol; Preventol O extra; Remol TRF; Tetrosin OE; Tetrosin OE-N; Torsite; Tumescal OPE; o-Xenol CAS Registry Number: 90-43-7 RTECS® Number: DV5775000 UN/NA & ERG Number: UN3143 Dyes, solid, toxic, n.o.s. [or] Dye intermediates, solid, toxic, n.o.s./151
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o-Phenylphenol
EC Number: 201-993-5 [Annex I Index No.: 604-020-00-6] Regulatory Authority and Advisory Bodies Carcinogenicity: NCI: Carcinogenesis Studies (derm); no evidence: rat; IARC: Animal Limited Evidence; Human Inadequate Evidence, not classifiable as carcinogenic to humans, Group 3, 1999. US EPA, FIFRA, 1998 Status of Pesticides: Supported. EPCRA Section 313 Form R de minimis concentration reporting level: 1.0%. California Proposition 65 Chemical: Cancer 8/4/00. Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: Hazard Symbol: Xi, N; Risk phrases: R36/37/38; R50; Safety phrases: S2; S22; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): 2—Hazard to waters. Description: o-Phenylphenol is a white to buff-colored crystalline solid. Molecular weight 5 170.22; Boiling point 5 286 C; Freezing/Melting point 5 57 C; Flash point 5 124 C; Autoignition temperature 5 530 C. Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 1, Reactivity 0. Slightly soluble in water. Potential Exposure: Compound Description: Agricultural Chemical; Tumorigen, Mutagen; Reproductive Effector; Primary Irritant. o-Phenylphenol is used in the manufacture of plastics, resins, rubber, as agricultural chemical; in making fungicides; as an intermediate in making dye stuffs and rubber chemicals; a germicide; used in food packaging. Incompatibilities: Strong bases, strong oxidizers. Permissible Exposure Limits in Air Protective Action Criteria (PAC) TEEL-0: 60 mg/m3 PAC-1: 150 mg/m3 PAC-2: 500 mg/m3 PAC-3: 500 mg/m3 DFG MAK: No numerical value established. Data may be available. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Irritates the eyes, skin, and respiratory tract. High exposures may affect the kidney, liver, and lungs; gastrointestinal tract; cardiovascular system, causing respiratory failure. Inhalation: Dusts can cause irritation of the nose, throat, and lungs. Skin: Can cause severe irritation and burns. Concentrations of 0.5% or higher of the sodium form can cause irritation. Eyes: Can cause severe irritation, burns, and damage to cornea, especially the sodium form. Ingestion: Based on studies of phenol, can cause burning sensation and pain in mouth and throat, sores, abdominal pain, nausea, vomiting, diarrhea, and skin rash. Larger doses may also cause muscle weakness, irregular rapid breathing, blue coloration of the skin, shock, unconsciousness, collapse, and death. Based on animal studies, 5 oz would be lethal to a 150-lb healthy adult.
Long Term Exposure: May cause kidney damage. Prolonged skin contact may cause severe irritation, sores, and skin allergy. Very irritating substances may affect the lungs; bronchitis may develop. Points of Attack: Lungs, kidneys, skin. Medical Surveillance: Before beginning employment and at regular times after that, for those with frequent or potentially high exposures, the following are recommended: lung function tests. Consider chest X-ray following acute overexposure. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Where there is potential for exposures to o-phenylphenol, use a NIOSH/MSHA- or European Standard EN149-approved full face-piece respirator with a high-efficiency particulate filter. Greater protection is provided by a powered air-purifying respirator. Where there is potential for high exposures, use a NIOSH/MSHA- or European Standard EN149-approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuous-flow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in pressure-demand or other positive-pressure mode. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, well-ventilated area away from water. Sources of ignition, such as smoking and open flames, are prohibited where o-phenylphenol is used, handled, or stored in a manner that could create a potential fire or explosion hazard. A regulated,
Phenylphosphine marked area should be established where this chemical is handled, used, or stored in compliance with OSHA Standard 1910.1045. Shipping: Dye intermediates, solid, toxic, n.o.s. requires a shipping label of “POISONOUS/TOXIC MATERIALS.” They fall in Hazard Class 6.1. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible solid. Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Poisonous gases are produced in fire. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: In accordance with 40CFR165, follow recommendations for the disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by contacting your local or federal environmental control agency or by contacting your regional EPA office. References New York State Department of Health. (April 1986). Chemical Fact Sheet ortho-Phenylphenol. Albany, NY: Bureau of Toxic Substance Assessment New Jersey Department of Health and Senior Services. (December 2000). Hazardous Substances Fact Sheet: oPhenylphenol. Trenton, NJ
Phenylphosphine Molecular Formula: C6H7P Common Formula: C6H5PH2 Synonyms: Fenylfosfin; PF; Phosphaniline CAS Registry Number: 638-21-1
P:0480
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RTECS® Number: SZ2100000 EC Number: 211-325-4 Regulatory Authority and Advisory Bodies Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. California Proposition 65 Developmental/Reproductive toxin 8/7/09. Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: not listed in Annex 1. WGK (German Aquatic Hazard Class): No value assigned. Description: Polyphosphinate is a clear, colorless liquid with a foul odor. Molecular weight 5 110.10; Specific gravity (H2O:1) 5 1.001 at 15 C; Boiling point 5 160 C. Insoluble in water; reacts. Potential Exposure: Polyphosphinate is used as an intermediate or a chemical reagent. Polyphosphinate compounds are used as catalysts and antioxidants disproportionate, when heated to give phosphonic acid derivatives plus PF. Incompatibilities: A strong reducing agent. Reacts violently with strong oxidizers. Water reactive; spontaneously combustible in high concentrations in moist air. Potential exposure to gaseous phenylphosphine and phosphorus oxides when heated above 200 C. Permissible Exposure Limits in Air Conversion factor: 1 ppm 5 4.50 mg/m3 at 25 C & 1 atm. OSHA PEL: None. NIOSH REL: 0.05 ppm/0.25 mg/m3 Ceiling Concentration. ACGIH TLV®[1]: 0.05 ppm/0.23 mg/m3 Ceiling Concentration. Protective Action Criteria (PAC) TEEL-0: 0.0025 ppm PAC-1: 0.0075 ppm PAC-2: 0.05 ppm PAC-3: 4 ppm Australia: TWA 0.05 ppm (0.25 mg/m3), 1993; Belgium: STEL 0.05 ppm (0.23 mg/m3), 1993; Denmark: TWA 0.05 ppm (0.25 mg/m3), 1999; Finland: STEL 0.05 ppm (0.25 mg/m3), 1999; France: VLE 0.05 ppm (0.25 mg/m3), 1999; Switzerland: MAK-W 0.05 ppm (0.25 mg/m3), 1999; the Netherlands: MAC 0.25 mg/m3, 2003; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: Ceiling Concentration 0.05 ppm. Several states have set guidelines or standards for PF in ambient air[60] ranging from 2.0 μg/m3 (Virginia) to 2.5 μg/m3 (North Dakota) to 6.0 μg/m3 (Nevada). Determination in Air: No method available. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: A level of 0.6 ppm is a threshold effect level for laboratory animals; hypersensitivity to sound and touch and mild hyperemia developed above this level. Above 2.2 ppm, chronic effects developed including decreases in red blood cells, dermatitis, and severe testicular degeneration (which was, however, reversible).[53] This
2124
Phenylthiourea
material is highly toxic by inhalation and ingestion; mild respiratory irritant; emits toxic fumes of phosphorus oxides when heated to decomposition. Symptoms of exposure include mild respiratory irritation, dyspnea, nausea, vomiting, diarrhea, thirst, sensation of pressure in the chest, back pains, chills, stupor, and fainting with marked pulmonary edema. Phenylphosphine can affect you when breathed in. Exposure can cause nausea, loss of appetite, shaking (tremor), irritation of the eyes, and flushed skin. Long Term Exposure: Repeated exposure can cause skin rash. Phenylphosphine can damage the blood cells. In animals: blood changes; anemia, testicular degeneration; loss of appetite; diarrhea, lacrimation (discharge of tears), hind leg tremor; dermatitis. Points of Attack: Blood, central nervous system, skin, reproductive system. Medical Surveillance: If symptoms develop or overexposure is suspected, the following may be useful: complete blood count. Examination of the nervous system. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Where there is potential for exposures over 0.05 ppm, use a NIOSH/MSHA- or European Standard EN149-approved supplied-air respirator with a full facepiece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuous-flow mode; or use a NIOSH/MSHA- or European Standard EN149approved self-contained breathing apparatus with a full face-piece operated in pressure-demand or other positivepressure mode. Storage: Pyrophoric. Color Code—Yellow Stripe (strong reducing agent): Reactivity Hazard; Store separately in an
area isolated from flammables, combustibles, or other yellow-coded materials. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, well-ventilated area. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Ventilate area of spill or leak. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a flammable liquid. Poisonous gases, including phosphorus oxides, are produced in fire. Use dry chemical, carbon dioxide, or alcohol foam extinguishers. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Reference New Jersey Department of Health and Senior Services. (July 2001). Hazardous Substances Fact Sheet: Phenylphosphine. Trenton, NJ
Phenylthiourea
P:0490
Molecular Formula: C7H8N2S Common Formula: C6H5NCHCSNH2 Synonyms: NCI-C02017; Phenylthiocarbamide; N-phenylthiourea; α-Phenylthiourea; Phenyl-2-thiourea; 1-Phenylthiourea; PTC; PTU
Phenylthiourea CAS Registry Number: 103-85-5 RTECS® Number: YU1400000 UN/NA & ERG Number: UN2767/151 EC Number: 203-151-2 Regulatory Authority and Advisory Bodies US EPA Hazardous Waste Number (RCRA No.): P093. RCRA, 40CFR261, Appendix 8 Hazardous Constituents. Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 100/10,000 lb (45.4/4540 kg). Reportable Quantity (RQ): 100 lb (45.4 kg). European/International Regulations: Hazard Symbol: Xn, N; Risk phrases: R36/38; R43; R51/53; Safety phrases: S28; S36/37-45 (see Appendix 4). WGK (German Aquatic Hazard Class): No value assigned. Description: N-phenylthiourea is a colorless crystalline solid. Molecular weight 5 152.23; Freezing/Melting point 5 148154 C. Soluble in water. Potential Exposure: Used as a repellent for rats, rabbits, and weasels; in the manufacture of rodenticides and in medical genetics. Incompatibilities: Incompatible with oxidizers, strong bases, and acids. Contact with acids or acid fumes produces toxic fumes of sulfur oxide. Permissible Exposure Limits in Air Protective Action Criteria (PAC) TEEL-0: 0.6 mg/m3 PAC-1: 1.5 mg/m3 PAC-2: 3 mg/m3 PAC-3: 3 mg/m3 Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Irritates the eyes, skin, and respiratory tract. High exposures can cause lung irritation, coughing, and/or shortness of breath. Higher exposures can cause pulmonary edema, a medical emergency that can be delayed for several hours. This can cause death. Exposure may result in vomiting, difficult breathing, noisy breathing, cyanosis, and low body temperature. It is classified as extremely toxic. The probable oral lethal dose is 550 mg/ kg or between 7 drops and 1 teaspoon for a 70-kg (150 lb) person. Long Term Exposure: Not tested for long-term health effects. May cause methemoglobinemia, cyanosis, and anemia. Phenylthiourea is reported to be similar to ANTU. Points of Attack: Lungs. Medical Surveillance: Lung function tests. Blood methemogloblin level. Completed blood count (CBC). Consider chest X-ray following acute overexposure. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure,
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begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. Note to physician: Treat for methemoglobinemia. Spectrophotometry may be required for precise determination of levels of methemoglobin in urine. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in pressure-demand or other positive-pressure mode. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in a refrigerator or a cool, dry place. Shipping: Phenylurea pesticides, solid, toxic, n.o.s. requires a shipping label of “POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 6.1 and Packing Group I. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Dampen spilled material with alcohol to avoid dust or use HEPA vacuum or wet method to reduce dust during cleanup. Do not dry sweep. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up
2126
Phenyl trichlorosilane
spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible solid. Use dry chemical, carbon dioxide, water spray, alcohol foam or polymer foam extinguishers. Poisonous gases are produced in fire, including nitrogen oxides and sulfur oxides. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: In accordance with 40CFR165, follow recommendations for the disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by contacting your local or federal environmental control agency or by contacting your regional EPA office. References US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Phenylthiourea. Washington, DC: Chemical Emergency Preparedness Program New Jersey Department of Health and Senior Services. (August 1999). Hazardous Substances Fact Sheet: Phenylthiourea. Trenton, NJ
Phenyl trichlorosilane
P:0500
Molecular Formula: C6H5Cl3Si Synonyms: Phenylsilicon trichloride; Phenyl trichlorosilane; Silicon phenyl trichloride; Silane, trichlorophenyl-; Trichlorophenylsilane; Tricloro(fenil)silano (Spanish) CAS Registry Number: 98-13-5 RTECS® Number: VV6650000 UN/NA & ERG Number: UN1804/156 EC Number: 202-640-8 Regulatory Authority and Advisory Bodies Department of Homeland Security Screening Threshold Quantity (pounds): Sabotage/Contamination Hazard: A placarded amount (commercial grade). Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 500 lb (227 kg). Reportable Quantity (RQ): 500 lb (227 kg). US DOT 49CFR172.101, Inhalation Hazardous Chemical. WGK (German Aquatic Hazard Class): 1—Low hazard to waters.
Description: Phenyl trichlorosilane is a colorless to light yellow liquid. Molecular weight 5 211.55; Specific gravity 5 1.32 at 25 C; Boiling point 5 202 C; Flash point 5 80.6 C; 91 C (oc). Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 2, Reactivity 2 . Water reactive. Potential Exposure: Phenyl trichlorosilane is used to make silicones for water repellants, insulating resins, heatresistant paints, and as a laboratory reagent. Incompatibilities: May spontaneously ignite in air above flash point. Contact with water, steam, or moisture forms hydrogen chloride. Trichlorosilanes may react violently with strong oxidants, strong acids, bases, amines, alcohols, acetone, ammonia. Attacks many metals in the presence of water, releasing explosive hydrogen gas. Permissible Exposure Limits in Air Protective Action Criteria (PAC) TEEL-0: 0.2 ppm PAC-1: 0.6 ppm PAC-2: 7.3 ppm PAC-3: 33 ppm Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Corrosive to the eyes, skin, and respiratory tract. Eye contact may damage the corneas and cause blindness. Inhalation may cause throat to swell, causing suffocation; and may cause pulmonary edema, a medical emergency that can be delayed for several hours. This can cause death. Highly toxic; may cause death or permanent injury after short inhalation exposure to small quantity. Chemical burns to all exposed membranes and tissues with severe tissue destruction. Delayed: after oral exposure, stomach and intestines may perforate to be obstructed by scar tissue. Ingestion may cause mild to moderately severe oral and esophageal burns, with severe burns occurring in stomach. Perforations and peritonitis may occur. Severe irritation may produce spontaneous vomiting. Viscid white or blood-stained foamy mucus and threads of tissue may appear in mouth. Long Term Exposure: Many highly irritating substances can cause lung damage; bronchitis may develop. Points of Attack: Lungs. Medical Surveillance: For those with frequent or potentially high exposure, the following are recommended before beginning work and at regular times after that: lung function tests. If symptoms develop or overexposure is suspected, the following may be useful: lung function tests. Consider chest X-ray after acute overexposure. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 30 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure,
Phenyl trichlorosilane begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. If victim is conscious, administer water or milk; then give demulcents, such as milk, cornstarch, and water. Do not induce vomiting. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Where there is potential for exposure to phenyl trichlorosilane, use a NIOSH/MSHA- or European Standard EN149-approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuous-flow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in pressure-demand or other positive-pressure mode. Storage: Color Code—White: Corrosive or Contact Hazard; Store separately in a corrosion resistant location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, well-ventilated area away from water at temperatures below 50 C. Phenyl trichlorosilane can give off corrosive hydrogen chloride gas on contact with water, steam, or moisture. Sources of ignition, such as smoking and open flames, are prohibited where Phenyl trichlorosilane is used, handled, or stored in a manner that could create a potential fire or explosion hazard. Shipping: Phenyl trichlorosilane requires a shipping label of “CORROSIVE.” It falls in Hazard Class 8 and Packing Group II. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Ventilate area of spill or leak. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose
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of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Initial isolation and protective action distances Distances shown are likely to be affected during the first 30 min after materials are spilled and could increase with time. If more than one tank car, cargo tank, portable tank, or large cylinder involved in the incident is leaking, the protective action distance may need to be increased. You may need to seek emergency information from CHEMTREC at (800) 424-9300 or seek professional environmental engineering assistance from the US EPA Environmental Response Team at (908) 548-8730 (24-h response line). Small spills (From a small package or a small leak from a large package) when spilled in water First: Isolate in all directions (feet/meters) 100/30 Then: Protect persons downwind (miles/kilometers) Day 0.1/0.2 Night 0.1/0.2 Large spills (From a large package or from many small packages) First: Isolate in all directions (feet/meters) 200/60 Then: Protect persons downwind (miles/kilometers) Day 0.3/0.5 Night 1.0/1.5 Fire Extinguishing: This chemical is a combustible and corrosive liquid. Poisonous gases, including chlorine and hydrogen chloride, are produced in fire. Use dry chemical, carbon dioxide. Do not use water or hydrous agents. Full protective clothing, including self-contained breathing apparatus; coat, pants, gloves, boots; and bands around legs, arms, and waist, should be provided. No skin surface should be exposed. Move container from fire area if you can do so without risk. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. Do not get water inside containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode.
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Phenytoin
References US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Trichlorophenylsilane. Washington, DC: Chemical Emergency Preparedness Program New Jersey Department of Health and Senior Services. (May 2000). Hazardous Substances Fact Sheet: Phenyl Trichlorosilane. Trenton, NJ
Phenytoin
P:0510
Molecular Formula: C15H12N2O2 Synonyms: AI3-52498; Aleviatin; Antisacer; Auranile; Causoin; Citrullamon; Citrulliamon; Comital; Comitoina; Convul; Danten; Dantinal; Dantoinal; Dantoinal klinos; Dantoine; Denyl; Didan TDC 250; Difenilhidantoina (Spanish); Difenin; Difhydan; Dihycon; di-Hydan; Dihydantoin; di-Lan; Dilantin acid; Dilantine; Dillantin; Dintion; Diphantoin; Diphedal; Diphenine; Diphentoin; Diphentyn; Diphenylan; 5,5-Diphenylhydantoin; Diphenylhydantoin; 5,5-Diphenylimidazolidin-2,4-dione; 5,5-Diphenyl-2,4-imida zolidinedione; Diphenylhydantoine; di-Phetine; Ditoinate; DPH; EKKO; EKKO Capsules; Enkelfel; Elepsindon; Epamin; Epanutin; Epasmir 5; Epdantoine simple; Epelin; Epilan; Epilantin; Epinat; Epised; Eptal; Eptoin; Fenantoin; Fenidantoin S; Fenitoina; Fenylepsin; Fenytoine; Gerot-epilan-D; Hidan; Hidantilo; Hidantina; Hidantina senosian; Hidantina vitoria; Hidantomin; Hydantoin; Hydantoin, 5,5-diphenyl-; Hydantoinal; Ictalis simple; Idantoin 2,4-imidazolidinedione, 5,5-diphenyl-; Kessodanten; Labopal; Lehydan; Lepitoin; Lepsin; Minetoin; NCI-C55765; Neos-hidantoina; Neosidantoina; Novantoina; OM-hidantoine simple; OMhydantoine; Oxylan; Phanantin; Phanatine; Phenatine; Phenatoine; Phenitoin; Ritmenal; Saceril; Sanepil; Silantin; Sodanthon; Sodantoin; Solantoin; Sylantoic; Tacosal; Thilophenyl; Toin; Toin unicelles; Zentronal; Zentropil CAS Registry Number: 57-41-0; 630-93-3 (sodium salt) RTECS® Number: MU1050000 UN/NA & ERG Number: UN3249 (Medicines, toxic, solid, n.o.s.)/151 EC Number: 200-328-6; 211-148-2 (phenytoin sodium) Regulatory Authority and Advisory Bodies Carcinogenicity: IARC: Human Limited Evidence, animal Sufficient Evidence, possibly carcinogenic to humans, Group 2B, 1987; NTP: Reasonably anticipated to be a human carcinogen. Clean Air Act: Accidental Release Prevention/Flammable Substances, (Section 112[r], Table 3), TQ 5 15,000 lb (6810 kg). US EPA Hazardous Waste Number (RCRA No.): U098. RCRA, 40CFR261, Appendix 8 Hazardous Constituents. EPCRA Section 313 Form R de minimis concentration reporting level: 0.1%.
Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 1000 lb (454 kg). Reportable Quantity (RQ): 10 lb (4.54 kg). California Proposition 65 Chemical: Cancer 1/1/88; Reproductive toxin 7/1/87; Cancer 1/1/88 (sodium salt). European/International Regulations: not listed in Annex 1. WGK (German Aquatic Hazard Class): No value assigned. Description: Phenytoin is a crystalline compound. Molecular weight 5 252.29; Freezing/Melting point 5 295298 C; Ignition temperature 5 585 C. May react with water. Potential Exposure: Phenytoin is a pharmaceutical used in the treatment of grand mal epilepsy, Parkinson’s syndrome; and in veterinary medicine. Human exposure to phenytoin occurs principally during its use as a drug. Figures on the number of patients using phenytoin are not available, but phenytoin is given to a major segment of those individuals with epilepsy. The oral dose rate is initially 100 mg given 3 times per day and can gradually increase by 100 mg every 24 weeks until the desired therapeutic response is obtained. The intravenous dose is 200350 mg/day. Incompatibilities: Strong acids, strong oxidizers, water. Permissible Exposure Limits in Air No standards or TEEL available. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Symptoms of exposure include blurred vision, hyperactivity, confusion, drowsiness, nausea, vomiting, epigastric pain, swelling of gums, fever, liver and kidney damage. Long Term Exposure: Phenytoin is carcinogenic in mice after oral administration or by intraperitoneal injection, producing lymphomas and leukemias. Points of Attack: Liver, kidneys. Medical Surveillance: Liver and kidney function tests. First Aid: Skin Contact[52]: Flood all areas of body that have contacted the substance with water. Do not wait to remove contaminated clothing; do it under the water stream. Use soap to help assure removal. Isolate contaminated clothing when removed to prevent contact by others. Eye Contact: Remove any contact lenses at once. Flush eyes well with copious quantities of water or normal saline for at least 2030 min. Seek medical attention. Inhalation: Leave contaminated area immediately; breathe fresh air. Proper respiratory protection must be supplied to any rescuers. If coughing, difficult breathing, or any other symptoms develop, seek medical attention at once, even if symptoms develop many hours after exposure. Ingestion: If convulsions are not present, give a glass or two of water or milk to dilute the substance. Assure that the person’s airway is unobstructed and contact a hospital or poison center immediately for advice on whether or not to induce vomiting. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide
Phorate recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Specific respirator(s) have not been recommended by NIOSH. However, based on potential carcinogenicity, and where the potential exists for exposure, the following might be considered: At any detectable concentration: SCBAF: Pd,Pp (APF 5 10,000) (any NIOSH/MSHA- or European Standard EN 149-approved self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary, self-contained breathing apparatus operated in a pressuredemand or other positive-pressure mode). Escape: 100 F (APF 5 50) (any air-purifying, full-face-piece respirator with an N100, R100, or P100 filter) or SCBAE (any appropriate escape-type, self-contained breathing apparatus). Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in a cool, dry place or in a refrigerator. Protection from air, light, and moisture is recommended for long term storage.[52] A regulated, marked area should be established where this chemical is handled, used, or stored in compliance with OSHA Standard 1910.1045. Shipping: Medicine, solid, toxic, n.o.s. requires a shipping label of “POISONOUS/TOXIC MATERIALS.” This compound falls in Hazard Class 6.1 and Packing Group III. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources[52]: Dampen spilled material with alcohol to avoid dust, then transfer material to a suitable container. Use absorbent dampened with alcohol to pick up remaining material. Wash surfaces well with soap and water. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible solid. Use dry chemical, carbon dioxide, water spray, or alcohol
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foam extinguishers. Poisonous gases, including nitrogen oxides, are produced in fire. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Reference New Jersey Department of Health and Senior Services. (April 2001). Hazardous Substances Fact Sheet: Phenytoin. Trenton, NJ
Phorate
P:0520
Molecular Formula: C7H17O2PS3 Synonyms: Aastar; AC3911; American cyanamid 3,911; O, O-Diaethyl-S-(aethylthio-methyl)-dithiophosphat (German); O,O-Diethyl S-ethylmercaptomethyl dithiophosphonate; O, O-Diethyl S-ethylthiomethyl dithiophosphonate; O,ODiethyl S-(ethylthio)methyl phosphorodithioate; O,ODiethyl S-[(ethylthio)methyl] phosphorodithioate; O, O-Diethylethylthiomethyl phosphorodithioate; O,O-Diethyl S-ethylthiomethyl thiothionophosphate; Dithiophosphatede O,O-diethyle et d’ethylthiomethyle (French); EL3911; ENT 24,042; Experimental insecticide 3911; Forato (Spanish); Geomet; Gramtox; Granutox; L11/6; Methanethiol, ethylthio-S-ester with O,O-diethyl phosphorodithioate; Phorat (German); Phorate-10G; Rampart; Terrathion granules; the met®; Thimet®; Vegfru; Vergfru Foratox CAS Registry Number: 298-02-2 RTECS® Number: TD9450000 UN/NA & ERG Number: UN3018 (organophosphorus pesticide, liquid, toxic)/152 EC Number: 206-052-2 [Annex I Index No.: 015-033-00-6] Regulatory Authority and Advisory Bodies US EPA Gene-Tox Program, Negative: D. melanogaster sex-linked lethal; Negative: In vitro UDS—human fibroblast; TRP reversion; Negative: S. cerevisiae—homozygosis; Inconclusive: B. subtilis rec assay; E. coli polA without S9; Inconclusive: Histidine reversion—Ames test. US EPA, FIFRA, 1998 Status of Pesticides: Supported. Banned or Severely Restricted (Malaysia) (UN).[13] Very Toxic Substance (World Bank).[15] Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. US EPA Hazardous Waste Number (RCRA No.): P094. RCRA, 40CFR261, Appendix 8 Hazardous Constituents.
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Phorate
RCRA 40CFR268.48; 61FR15654, Universal Treatment Standards: Wastewater (mg/L), 0.021; Nonwastewater (mg/ kg), 4.6. RCRA 40CFR264, Appendix 9; TSD Facilities Ground Water Monitoring List. Suggested test method(s) (PQL μg/ L): 8140 (2); 8270 (10). Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 10 lb (4.54 kg). Reportable Quantity (RQ): 10 lb (4.54 kg). US DOT Regulated Marine Pollutant (49CFR172.101, Appendix B), severe pollutant. US DOT 49CFR172.101, Inhalation Hazard Chemical as organophosphates. European/International Regulations: Hazard Symbol: T1, N; Risk phrases: R27/28; R50/53 Safety phrases: S1/2; S28; S36/37; S45; S60; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): No value assigned. Description: Phorate is a clear mobile liquid with a skunklike odor. Molecular weight 5 260.39; Specific gravity (H2O:1) 5 1.16 at 25 C; Boiling point 5 118120 C at 0.8 mm; Freezing/Melting point 5 42.8 C; Vapor pressure 5 0.0008 at 20 C; Flash point 5 160 C. Hazard Identification (based on NFPA-704 M Rating System): Health 4, Flammability 1, Reactivity 0. Practically insoluble in water; solubility 5 0.005%. Potential Exposure: Compound Description: Agricultural Chemical; Mutagen; Reproductive Effector; Human Data; Primary Irritant. Those engaged in the manufacture, formulation, and application of this systemic and contact insecticide and acaricide. It is also used as a soil insecticide. Incompatibilities: Water, alkalis. Hydrolyzed in the presence of moisture and by alkalis; may produce toxic oxides of phosphorus and sulfur. Strong oxidizers may cause release of toxic phosphorus oxides. Organophosphates, in the presence of strong reducing agents such as hydrides, may form highly toxic and flammable phosphine gas. Keep away from alkaline materials. Permissible Exposure Limits in Air OSHA PEL: None. NIOSH REL: 0.05 mg/m3 TWA; 0.2 mg/m3 STEL [skin]. ACGIH TLV®[1]: 0.05 mg/m3 TWA, inhalable fraction and vapor; [skin] not classifiable as a human carcinogen; BEIA issued for Acetylcholinesterase inhibiting pesticides. Protective Action Criteria (PAC)* TEEL-0: 0.04 mg/m3 PAC-1: 0.04 mg/m3 PAC-2: 0.040 mg/m3 PAC-3: 0.12 mg/m3 AEGLs (Acute Emergency Guideline Levels) & ERPGs (Emergency Response Planning Guideline) are in bold face. Australia: TWA 0.05 mg/m3; STEL 0.2 mg/m3, [skin], 1993; Belgium: TWA 0.05 mg/m3, [skin], 1993; Denmark: TWA 0.05 mg/m3, [skin], 1999; France: VME 0.05 mg/m3, [skin], 1999; Norway: TWA 0.05 mg/m3, 1999; Switzerland: MAK-W 0.05 mg/m3, [skin], 1999; United
Kingdom: TWA 0.05 mg/m3; STEL 0.2 mg/m3, [skin], 2000; the Netherlands: MAC-TGG 0.05 mg/m3, [skin], 2003; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: STEL 0.2 mg/m3 [skin]. Several states have set guidelines or standards for Phorate in ambient air[60] ranging from 0.52.0 μg/m3 (North Dakota) to 0.8 μg/m3 (Virginia) to 1.0 μg/m3 (Connecticut and Nevada). Determination in Air: Use NIOSH Analytical Method (IV) #5600, Organophosphorus pesticides. Permissible Concentration in Water: Maine[61] has set a guideline for phorate in drinking water of 0.2 μg/L. Determination in Water: Fish Tox 5 0.13505000 ppb (EXTRA HIGH). Octanolwater coefficient: Log Kow 5 3.88. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Absorbed through the skin. Harmful Effects and Symptoms Short Term Exposure: Acute exposure to phorate may produce the following signs and symptoms: pinpoint pupils, blurred vision, headache, dizziness, muscle spasms, and profound weakness. Vomiting, diarrhea, abdominal pain, seizures, and coma may also occur. The heart rate may decrease following oral exposure or increase following dermal exposure. Chest pain may be noted. Hypotension (low blood pressure) may occur, although hypertension (high blood pressure) is not uncommon. Dyspnea (shortness of breath) may be followed by respiratory collapse. Giddiness is common. This material is one of the most toxic organophosphorus insecticides. It is a cholinesterase inhibitor that acts on the nervous system; and produces toxicity similar to parathion. The probable oral lethal dose for humans is less than 5 mg/kg, i.e., a taste (less than 7 drops) for a 70-kg (150 lb) person. LD50 5 (oral-rat) 37 mg/kg. Long Term Exposure: Cholinesterase inhibitor; cumulative effect is possible. This chemical may damage the nervous system with repeated exposure; resulting in convulsions, respiratory failure. May cause liver damage. Human Tox 5 3.50000 ppm (HIGH). Points of Attack: Respiratory system, lungs, central nervous system, cardiovascular system, skin, eyes, plasma and red blood cell cholinesterase. Medical Surveillance: Before employment and at regular times after that, the following are recommended: plasma and red blood cell cholinesterase levels (tests for the enzyme poisoned by this chemical). If exposure stops, plasma levels return to normal in 12 weeks while red blood cell levels may be reduced for 13 months. Do not drink any alcoholic beverages before or during use. Alcohol promotes absorption of organic phosphates. When cholinesterase enzyme levels are reduced by 25% or more below preemployment levels, risk of poisoning is increased, even if results are in lower ranges of “normal.” Reassignment to work not involving organophosphate or carbamate pesticides is recommended until enzyme levels recover. If symptoms develop or overexposure occurs,
Phorate repeat the above tests as soon as possible and get an examination of the nervous system. Also consider complete blood count. Consider chest X-ray following acute overexposure. Do not drink any alcoholic beverages before or during use. Alcohol promotes absorption of organic phosphates. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Speed in removing material from skin is of extreme importance. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Not available according to NIOSH. The following is included for reference: NIOSH: (parathion) 0.5 mg/m3: CcrOv95 (APF 5 10) [any air-purifying half-mask respirator with organic vapor cartridge(s) in combination with an N95, R95, or P95 filter. The following filters may also be used: N99, R99, P99, N100, R100, P100] or Sa (APF 5 10) (any supplied-air respirator). 1.25 mg/m3: Sa:Cf (APF 5 25) (any supplied-air respirator operated in a continuous-flow mode) or PaprOvHie (APF 5 25) (any powered air-purifying respirator with an organic vapor cartridge in combination with a high-efficiency particulate filter). 2.5 mg/m3: CcrFOv100 (APF 5 50) [any air-purifying full-face-piece respirator equipped with organic vapor cartridge(s) in combination with an N100, R100, or P100 filter] or SaT: Cf (APF 5 50) (any supplied-air respirator that has a tight-fitting face-piece and is operated in a continuousflow mode) or PaprTOvHie (APF 5 50) [any powered, airpurifying respirator with a tight-fitting face-piece and organic vapor cartridge(s) in combination with a highefficiency particulate filter] or SCBAF (APF 5 50) (any self-contained breathing apparatus with full face-piece) or SaF (APF 5 50) (any supplied-air respirator with a full face-piece). 10 mg/m3: Sa: Pd,Pp (APF 5 1000) (any supplied-air respirator operated in a pressure-demand or other
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positive-pressure mode). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd, Pp (APF 5 10,000) (any self-contained breathing apparatus that has a full face-piece and is operated in a pressuredemand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: GmFOv100 (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or backmounted organic vapor canister having an N100, R100, or P100 filter] or SCBAE (any appropriate escape-type, selfcontained breathing apparatus). Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, well-ventilated area away from water and alkalis. Where possible, automatically pump liquid from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of 5 gallons or more of this chemical should be grounded and bonded. Drums must be equipped with self-closing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosionproof electrical equipment and fittings. Shipping: Organophosphorus pesticides, liquid, toxic, n.o.s. requires a shipping label of “POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 6.1 and Packing Group I. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Ventilate area of spill or leak. Stay upwind; keep out of low areas. Ventilate closed spaces before entering them. Remove and isolate contaminated clothing at the site. Do not touch spilled material; stop leak if you can do it without risk. Use water spray to reduce vapors. Small spills: take up with sand or other noncombustible absorbent material and place into containers for later disposal. Large spills: dike far ahead of spill for later disposal. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable.
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Phosacetim
Fire Extinguishing: This chemical is a combustible liquid. Poisonous gases, including nitrogen oxides, phosphorous oxides, sulfur oxides, are produced in fire. Use dry chemical, carbon dioxide, or alcohol foam extinguishers. Wear positive pressure self-contained breathing apparatus. Move container from fire area if you can do it without risk. Fight fire from maximum distance. Dike fire control water for later disposal; do not scatter the material. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: In accordance with 40CFR165, follow recommendations for the disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by contacting your local or federal environmental control agency or by contacting your regional EPA office. Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant ($100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. References US Environmental Protection Agency. (April 30, 1980). Phorate: Health and Environmental Effects Profile No. 145. Washington, DC: Office of Solid Waste US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Phorate. Washington, DC: Chemical Emergency Preparedness Program New Jersey Department of Health and Senior Services. (September 2001). Hazardous Substances Fact Sheet: Phorate. Trenton, NJ
Phosacetim
P:0530
Molecular Formula: C14H13Cl2N2O2PS Synonyms: Acetimidoylphosphoramidothioic acid O,O-bis (p-chlorophenyl) ester; BAY 33819; Bayer 33819; O,O-Bis
(p-chlorophenyl) acetimidoyl phosphoramidothioate; O,O-Bis (4-chlorophenyl) N-acetimidoyl phosphoramidothioate; O,OBis(4-chlorophenyl) 1-iminoethyl phosphoramidothioate; O, O-Bis(4-chlorophenyl)-1-iminoethylphosphoramidothioic acid; DRC-714; Gophacide; (1-Iminoethyl)phosphoramidothioic acid, O,O-bis(4-chlorophenyl) ester; Phosazetim; Phosphonodithio-imidocarbonic acid, acetimidoyl-, O,O-bis (p-chlorophenyl) ester; Phosphonodithioimidocarbonic acid, (1-iminoethyl)-, O,O-bis(p-chlorophenyl) ester CAS Registry Number: 4104-14-7 RTECS® Number: TB4725000 UN/NA & ERG Number: UN2783 (organophosphorus pesticides, solid, toxic)/152 EC Number: 223-874-7 [Annex I Index No.: 015-092-00-8] Regulatory Authority and Advisory Bodies Banned or Severely Restricted (East Germany, Philippines) (UN).[13] Very Toxic Substance (World Bank).[15] Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 100/10,000 lb (45.4/4540 kg). Reportable Quantity (RQ): 100 lb (45.4 kg). US DOT 49CFR172.101, Inhalation Hazard Chemical as organophosphates. European/International Regulations: Hazard Symbol: T1, N; Risk phrases: R27/28; R50/53; Safety phrases: S1/2; S28; S36/37; S45; S60; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): No value assigned. Description: Phosacetim is a crystalline solid. Molecular weight 5 375.22. Hazard Identification (based on NFPA704 M Rating System): Health 4 Flammability 1, Reactivity 0. Potential Exposure: Used as a rodenticide. Incompatibilities: Strong oxidizers, nitrates. May hydrolyze on contact with moisture. Permissible Exposure Limits in Air Protective Action Criteria (PAC) TEEL-0: 0.75 mg/m3 PAC-1: 2 mg/m3 PAC-2: 3.7 mg/m3 PAC-3: 3.7 mg/m3 Determination in Air: Use NIOSH Analytical Method (IV) #5600, Organophosphorus Pesticides. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Absorbed by the skin. Harmful Effects and Symptoms Short Term Exposure: Organic phosphorus insecticides are absorbed by the skin as well as by the respiratory and gastrointestinal tracts. They are cholinesterase inhibitors. Symptoms of exposure include headache, giddiness, blurred vision, nervousness, weakness, nausea, cramps, diarrhea, and discomfort in the chest. Signs include sweating, tearing, salivation, vomiting, cyanosis, convulsions, coma, loss of reflexes, and loss of sphincter control. Highly toxic. LD50 oral rat is 3.7 mg/kg. Long Term Exposure: Cholinesterase inhibitor; cumulative effect is possible. This chemical may damage the nervous
Phosacetim system with repeated exposure, resulting in convulsions and respiratory failure. May cause liver damage. Points of Attack: Respiratory system, lungs, central nervous system, cardiovascular system, skin, eyes, plasma and red blood cell cholinesterase. Medical Surveillance: Before employment and at regular times after that, the following are recommended: plasma and red blood cell cholinesterase levels (tests for the enzyme poisoned by this chemical). If exposure stops, plasma levels return to normal in 12 weeks while red blood cell levels may be reduced for 13 months. When cholinesterase enzyme levels are reduced by 25% or more below preemployment levels, risk of poisoning is increased, even if results are in lower ranges of “normal.” Reassignment to work not involving organophosphate or carbamate pesticides is recommended until enzyme levels recover. If symptoms develop or overexposure occurs, repeat the above tests as soon as possible and get an examination of the nervous system. Also consider complete blood count. Consider chest X-ray following acute overexposure. Do not drink any alcoholic beverages before or during use. Alcohol promotes absorption of organic phosphates. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Speed in removing material from skin is of extreme importance. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard
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EN149-approved self-contained breathing apparatus with a full face-piece operated in pressure-demand or other positive-pressure mode. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Shipping: Organophosphorus pesticides, solid, toxic, requires a shipping label of “POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 6.1 and Packing Group I. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a flammable solid. Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Poisonous gases are produced in fire, including oxides of phosphorus, sulfur, nitrogen, and chlorine. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant ($100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. In accordance with 40CFR165, follow recommendations for the disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by contacting your local or federal environmental control agency or by contacting your regional EPA office. Reference US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Phosacetim. Washington, DC: Chemical Emergency Preparedness Program
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Phosfolan
Phosfolan
P:0540
Molecular Formula: C7H14NO3PS2 Synonyms: AC 47031; American cyanamid 47031; C.I. 47031; Cyclic ethylene(diethoxyphosphinothioyl)-dithioimidocarbonate; Cyclic ethylene p,p-diethylphosphono dithioimidocarbonate; Cylan; Cyolane; Cyolane insecticide; (Diethoxyphosphinyl)dithioimidocarbonic acid cyclic ethylene ester; 2-(Diethoxyphosphinylimino)-1,3-dithiolan; 2-(Diethoxyphosphinylimino)-1,3-dithiolane; p,p-Diethyl cyclic ethylene ester of phosphonodithioimidocarbonate; p, p-Diethyl cyclic ethylene ester of phosphonodithioimidocarbonic acid; Diethyl 1,3-dithiolan-2-ylidenephosphoramidate; EI 47031; ENT 25,830; 1,2-Ethanedithiol, cyclic ester with p,p-diethyl phosphonodithioimidocarbonate; 1,2-Ethanedithiol, cyclic ester with phosphonodithioimidocarbonic acid p,p-diethyl ester; Imidocarbonic acid, phosphonodithio-, cyclic ethylene p,p-diethyl ester; Phosphoroamidic acid, 1,3-dithiolan-2-ylidene-, diethyl ester CAS Registry Number: 947-02-4 RTECS® Number: NJ6475000 UN/NA & ERG Number: UN2783 (organophosphorus pesticides, solid, toxic)/152 EC Number: 213-423-2 [Annex I Index No.: 015-111-00-X] Regulatory Authority and Advisory Bodies Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 100/10,000 lb (45.4/4540 kg). Reportable Quantity (RQ): 100 lb (45.4 kg). US DOT 49CFR172.101, Inhalation Hazard Chemical as organophosphates. European/International Regulations: Hazard Symbol: T1, N; Risk phrases: R27/28; Safety phrases: S1/2; S28; S36/ 37; S45 (see Appendix 4). WGK (German Aquatic Hazard Class): No value assigned. Description: Phosfolan is a colorless to yellow solid. Molecular weight 5 255.31; Boiling point 5 115118 C at 0.001 mm; Freezing/Melting point 5 3745 C. Hazard Identification (based on NFPA-704 M Rating System): Health 4, Flammability 1, Reactivity 0. Soluble in water. Potential Exposure: Those involved in the manufacture, formulation, and application of this insecticide. Incompatibilities: Incompatible with nitrates and water. May hydrolyze upon contact with water, steam, and moisture, and produce toxic oxides of phosphorus, nitrogen, sulfur, and chlorine. Permissible Exposure Limits in Air Protective Action Criteria (PAC) TEEL-0: 1.5 mg/m3 PAC-1: 5 mg/m3 PAC-2: 9 mg/m3 PAC-3: 9 mg/m3 Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Absorbed through the skin.
Harmful Effects and Symptoms Short Term Exposure: Similar to parathion in health hazards. Death may result due to respiratory arrest as a result of paralysis of respiratory muscles and intense bronchoconstriction. Also considered a cholinesterase inhibitor. Symptoms similar to parathion include nausea, vomiting, abdominal cramps, diarrhea, excessive salivation, headache, giddiness, dizziness, tightness in the chest, blurring or dimness of vision, tearing, loss of muscle coordination, slurring of speech, twitching of muscles, drowsiness, difficulty in breathing, respiratory rales, and random jerky movements. Long Term Exposure: Cholinesterase inhibitor; cumulative effect is possible. This chemical may damage the nervous system with repeated exposure, resulting in convulsions, respiratory failure. May cause liver damage. Points of Attack: Respiratory system, lungs, central nervous system, cardiovascular system, skin, eyes, plasma and red blood cell cholinesterase. Medical Surveillance: Before employment and at regular times after that, the following are recommended: plasma and red blood cell cholinesterase levels (tests for the enzyme poisoned by this chemical). If exposure stops, plasma levels return to normal in 12 weeks while red blood cell levels may be reduced for 13 months. When cholinesterase enzyme levels are reduced by 25% or more below preemployment levels, risk of poisoning is increased, even if results are in lower ranges of “normal.” Reassignment to work not involving organophosphate or carbamate pesticides is recommended until enzyme levels recover. If symptoms develop or overexposure occurs, repeat the above tests as soon as possible and get an examination of the nervous system. Also consider complete blood count. Consider chest X-ray following acute overexposure. Do not drink any alcoholic beverages before or during use. Alcohol promotes absorption of organic phosphates. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Speed in removing material from skin is of extreme importance. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Keep victim quiet and maintain normal body temperature. Effects may be delayed; keep victim under observation. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing
Phosgene (Agents CG & DP, WMD) material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in pressure-demand or other positive-pressure mode. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, wellventilated area away from oxidizers, nitrates, and other incompatible materials listed above. Where possible, automatically transfer material from other storage containers to process containers. Shipping: Organophosphorus pesticides, solid, toxic, require a shipping label of “POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 6.1 and Packing Group I. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible solid. Extinguish with dry chemical, carbon dioxide, water spray, foam, or fog. Fight fire from maximum distance. Dike fire control water for later disposal; do not scatter the material. Wear positive pressure breathing apparatus and special protective clothing. Poisonous gases are produced in fire. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees
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are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant ($100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. In accordance with 40CFR165, follow recommendations for the disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by contacting your local or federal environmental control agency or by contacting your regional EPA office. Reference US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Phosfolan. Washington, DC: Chemical Emergency Preparedness Program
Phosgene (Agents CG & DP, WMD) P:0550 Molecular Formula: CCl2O Common Formula: COCl2 Synonyms: Carbone (oxychlorure de) (French); Carbon dichloride oxide; Carbon oxychloride; Carbonic dichloride; Carbon oxychloride; Carbonylchlorid (German); Carbonyl chloride; Carbonyl dichloride; CG (military designation); Chloroformyl chloride; Combat gas; Diphosgene; DP (military designation for diphosgene); Fosgeno (Spanish); NCIC60219; Phosgen (German); Trichloroacetyl chloride (diphosgene) CAS Registry Number: 75-44-5; 503-38-8 (diphosgene) RTECS® Number: SY5600000 UN/NA & ERG Number: UN1076/125 EC Number: 200-870-3 [Annex I Index No.: 006-002-00-8]; 207-965-9 (diphosgene or trichloromethyl chloroformate) Regulatory Authority and Advisory Bodies Department of Homeland Security Screening Threshold Quantity (pounds): Release hazard 500 (1.00% concentration); Theft hazard 15 ($0.17% concentration). Carcinogenicity: EPA: Inadequate Information to assess carcinogenic potential. Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Clean Air Act: Hazardous Air Pollutants (Title I, Part A, Section 112); List of high-risk pollutants (Section 63.74); Accidental Release Prevention/Flammable Substances, (Section 112[r], Table 3), TQ 5 500 lb (227 kg). Clean Water Act: Section 311 Hazardous Substances/RQ 40CFR117.3 (same as CERCLA, see below); Section 313 Water Priority Chemicals (57FR41331, 9/9/92).
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Phosgene (Agents CG & DP, WMD)
US EPA Hazardous Waste Number (RCRA No.): P095. RCRA, 40CFR261, Appendix 8 Hazardous Constituents. Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 10 lb (4.54 kg). Reportable Quantity (RQ): 10 lb (4.54 kg). EPCRA Section 313 Form R de minimis concentration reporting level: 1.0%. US DOT 49CFR172.101, Inhalation Hazardous Chemical. Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: Hazard Symbol (7544-5): T 1 ; Risk phrases: R26; R34; Safety phrases: S1/2; S9; S26; S36/37/39; S45 (see Appendix 4). WGK (German Aquatic Hazard Class): 2—Hazard to waters. Description: Phosgene (CG) is a colorless, noncombustible gas. It is shipped as a liquefied compressed gas in steel cylinders. At low concentrations CG has a sweet (not pleasant) odor like newly mown hay, green corn, or moldy hay. In higher concentrations, it is poisonous with an odor that is suffocating, irritating, and pungent. The odor is only detectable for a short amount of time when CG is initially released and odor should not be regarded as a reliable indicator of overexposure. A fuming liquid below 8.3 C/47 F. Shipped as a liquefied compressed gas. The odor threshold is between 1.5 and 6 mg/m3. A choking agent, phosgene (CG), rapidly decomposes in relative humidity over 70%. Molecular weight 5 98.92; Boiling point 5 8.2 C; Freezing/ Melting point 5 118 C; Relative vapor density (air 5 1) 5 3.48; Vapor pressure 5 1.61 atm at 25 C. Hazard Identification (based on NFPA-704 M Rating System): Health 4, Flammability 0, Reactivity 1. Reacts with water (slightly soluble). Potential Exposure: Compound Description: Human Data. Phosgene can be deadly at a concentration as low as 2 ppm. Phosgene is used as an intermediate in the manufacture of many industrial chemicals, including dyes and plastics; in the making of dyestuffs based on triphenylmethane, coal tar, and urea. It is also used in the organic synthesis of isocyanates and their derivatives, carbonic acid esters (polycarbonates), and acid chlorides. Other applications include its utilization in metallurgy; and in the manufacture of some insecticides and pharmaceuticals. Exposure to phosgene may occur during arc welding and in fires involving vinyl chloride; released from household paint removers and degreasers when they are used in the presence of heat. Phosgene (CG) has been used as a military choking, pulmonary agent since WW I, and has become a staple of chemical arsenals in many countries. Persistence of Chemical Agent: Phosgene (CG & DO): Summer: 110 min; Winter: 10 min to 1 h. Incompatibilities: Moisture, alkalis, ammonia, alcohols, copper. Reacts slowly in water to form hydrochloric acid and carbon dioxide. Violent reaction with strong oxidizers, amines, aluminum. Attacks many metals in the presence of water. Attacks plastic, rubber, and coatings.
Permissible Exposure Limits in Air Conversion factor: 1 ppm 5 4.05 mg/m3 at 25 C & 1 atm. OSHA PEL: 0.1 ppm/0.4 mg/m3 TWA. NIOSH REL: 0.1 ppm/0.4 mg/m3 TWA; 0.2 ppm/0.8 mg/ m3 [15 min] Ceiling Concentration. ACGIH TLV®[1]: 0.1 ppm/0.4 mg/m3 TWA. Protective Action Criteria (PAC) CG* TEEL-0: 0.1 ppm PAC-1: 0.1 ppm PAC-2: 0.3 ppm PAC-3: 0.75 ppm *AEGLs (Acute Emergency Guideline Levels) & ERPGs (Emergency Response Planning Guideline) are in bold face. NIOSH IDLH: 2 ppm. NIOSH IDLH: 2 ppm. Emergency Response Planning Guidelines (AIHA) ERPG-1: Inappropriate ERPG-2: 0.2 ppm ERPG-3: 1 ppm DFG MAK: 0.02 ppm; 0.082 mg/m3 TWA; Peak Limitation Category I(2); Pregnancy Risk Group C. Austria: MAK 0.1 ppm (0.4 mg/m3), 1999; Denmark: TWA 0.05 ppm (0.2 mg/m3), 1999; Finland: STEL 0.05 ppm (0.2 mg/m3), [skin], 1999; France: VLE 0.1 ppm (0.4 mg/ m3), 1999; Japan: 0.1 ppm (0.4 mg/m3), 1999; the Netherlands: MAC-TGG 0.08 mg/m3, 2003; the Philippines: TWA 0.1 ppm (0.1 mg/m3), 1993; Poland: MAC (TWA) 0.5 mg/m3; MAC (STEL) 1.5 mg/m3, 1999; Sweden: TGV 0.05 ppm (0.2 mg/m3), 1999; Switzerland: MAK-W 0.1 ppm (0.4 mg/m3), KZG-W 0.2 ppm (0.8 mg/m3), 1999; Thailand: TWA 0.1 ppm (0.4 mg/m3), 1993; Turkey: TWA 0.1 ppm (0.4 mg/m3), 1993; United Kingdom: TWA 0.02 ppm (0.08 mg/m3); STEL 0.06 ppm, 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: TWA 0.1 ppm. The Czech Republic has set a TWA of 0.5 mg/m3 and a ceiling value of 1.0 mg/m3 in work-place air, and MAC in ambient air of 0.01 mg/m3 and 0.003 mg/m3 on a daily average basis. Several states have set guidelines or standards for phosgene in ambient air[60] ranging from zero (North Carolina) to 1.33 μg/m3 (New York) to 4.0 μg/m3 (Florida, North Dakota, South Carolina) to 7.0 μg/m3 (Virginia) to 8.0 μg/m3 (Connecticut) to 10.0 μg/m3 (Nevada). Determination in Air: Use OSHA Analytical Method 61. Determination in Water: Octanolwater coefficient: Log Kow 5 0.71. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Acute exposure to phosgene may result in severe irritation and burns of the skin, eyes, mucous membranes, and respiratory passages. Cough, dyspnea (shortness of breath), pain in the chest, and severe pulmonary edema may also occur. Cyanosis and anxiety may be observed.
Phosgene (Agents CG & DP, WMD) Note: The detection of the odor of phosgene at any time indicates the need for immediate, corrective action or withdrawal. Inhalation: Both immediate and delayed symptoms may be felt. Immediate symptoms of irritation to mouth, throat, and eyes, tearing, coughing, and difficult breathing are felt at levels of 5 ppm and above. Delayed effects are the accumulation of fluid in the lungs and death; if proper, rapid treatment is not obtained. The length of delay depends on the dose but may be between 2 and 15 h. Death may result from short exposures to high levels (30 ppm, 17 min) or long exposures to low levels (3 ppm, 3 h). Phosgene is particularly dangerous at low levels because lethal doses may be inhaled without warning symptoms. Skin: Contact with skin may lead to severe chemical burns. Liquid may cause frostbite. Eyes: Eye irritation begins at 35 ppm. Severe and permanent damage may result. Liquid phosgene is more hazardous than vapor. Liquid may cause frostbite. Ingestion: Expected symptoms may include severe irritation and chemical burns of the mouth, throat, lungs, and digestive tract. Long Term Exposure: Even low levels can cause permanent lung damage, emphysema, bronchitis, pulmonary fibrosis. Points of Attack: Respiratory system, lungs, skin, eyes. Medical Surveillance: Preemployment medical examinations should include chest X-rays and baseline pulmonary function tests. Consider chest X-ray following acute overexposure. The eyes and skin should be examined. Smoking history should be known. Periodic pulmonary function studies should be done. Workers who are known to have inhaled phosgene should remain under medical observation for at least 24 h to insure that delayed symptoms do not occur. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately. If this chemical contacts the skin, flush with water immediately. If a person breathes in large amounts of this chemical, move the exposed person to fresh air at once and perform artificial respiration. When this chemical has been swallowed, get medical attention. Do not induce vomiting. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. If frostbite has occurred, seek medical attention immediately; do NOT rub the affected areas or flush them with water. In order to prevent further tissue damage, do NOT attempt to remove frozen clothing from frostbitten areas. If frostbite has NOT occurred, immediately and thoroughly wash contaminated skin with soap and water. Decontamination: Decontaminate as soon as possible. This is extremely important. If you do not have the equipment and training, do not enter the hot zone to rescue and/or decontaminate victims. If the victim cannot move, begin the decontamination process without touching and without entering the hot zone. Use clean water from any source; if possible, use a hose (spray or fog to prevent injury to the
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victim) or other system so that you would not have to touch the victim; do not even wait for soap or for the victim to remove clothing, begin washing immediately. Immediately flush the eyes with water for at least 15 min. Washstripwashevacuate upwind and uphill: The approach is to immediately wash with water, then have the victim (not the first responder) remove all the victim’s clothing, then wash again (with soap if available); and subsequently move away from the hot zone in an upwind and uphill direction. Wash the victim with warm water and soap. Decontaminate with diluted household bleach (10%, or one part bleach to nine parts water), but do not let any of the bleach solution get in the victim’s eyes, open wounds, or mouth. Rinse off the diluted bleach solution after 15 min. In order to prevent spreading the agent, be certain the victims have been decontaminated as much as possible before they leave the decontamination area. If you get any amount of the agent on yourself, decontaminate immediately. Even if you think you are not contaminated, be sure to thoroughly shower and change clothes as soon as you can after the incident. Personal Protective Methods: Where liquid phosgene is encountered, protective clothing should be supplied which is impervious to phosgene. Where gas is encountered above safe limits, full-face gas masks with phosgene canisters or supplied-air respirators should be used. Because of the potentially serious consequences of acute overexposure and the poor warning properties of the gas to the human senses, automatic continuous monitors with alarm systems are strongly recommended. Wear appropriate clothing to prevent any reasonable probability of skin contact. Wear eye protection to prevent any possibility of eye contact. Employees should wash immediately when skin is wet or contaminated. Remove nonimpervious clothing immediately if wet or contaminated. Provide emergency showers. Respirator Selection: 1 ppm: Sa (APF 5 10) (any suppliedair respirator). 2 ppm: SCBAF (APF 5 50) (any selfcontained breathing apparatus with a full face-piece) or SaF (APF 5 50) (any supplied-air respirator with a full facepiece). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd,Pp (APF 5 10,000) (any self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: GmFS (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or back-mounted canister providing protection against the compound of concern] or SCBAE (any appropriate escape-type, self-contained breathing apparatus). Note: Substance reported to cause eye irritation or damage; may require eye protection.
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Phosgene (Agents CG & DP, WMD)
Storage: Color Code—Yellow Stripe: Reactivity Hazard; Store separately in an area isolated from flammables, combustibles, or other yellow-coded materials. Color Code— Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Phosgene must be stored to avoid contact with water, moisture, or steam, since violent reactions occur. Store in tightly closed, steel containers in an isolated area away from the work area and separated from all other materials, as well as sunlight. Although phosgene in anhydrous equipment is not corrosive to ordinary metals; in the presence of moisture, use monel, tantalum, or glass-lined storage containers. Phosgene should be stored away from heating and cooling ducts. Containers should be frequently inspected for leaks. Procedures for the handling, use, and storage of cylinders should be in compliance with OSHA 1910.101 and 1910.169 with the recommendations of the Compressed Gas Association. Shipping: Phosgene requires a shipping label of “POISON GAS, CORROSIVE.” It falls in Hazard Class 2.3. It is a violation of transportation regulations to refill compressed gas cylinders without the express written permission of the owner. Special precautions: Cylinders must be transported in a secure upright position, in a well-ventilated truck. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Ventilate area of leak to disperse the gas. Stop flow of gas. If source of leak is a cylinder and the leak cannot be stopped in place, remove the leaking cylinder to a safe place in the open air, and repair leak or allow cylinder to empty. Absorb liquids in vermiculite, dry sand, earth, or a similar material and deposit in sealed containers. Phosgene may be neutralized by covering it with sodium bicarbonate or an equal mixture of soda ash and slaked lime. After mixing, spray very carefully with water. Transfer slowly to a larger container of water. Do not use water directly on spill. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Initial isolation and protective action distances Distances shown are likely to be affected during the first 30 min after materials are spilled and could increase with time. If more than one tank car, cargo tank, portable tank, or large cylinder involved in the incident is leaking, the protective action distance may need to be increased. You may need to seek emergency information from CHEMTREC at (800) 424-9300 or seek professional environmental engineering assistance from the US EPA Environmental Response Team at (908) 548-8730 (24-h response line).
CG, when used as a weapon Small spills (From a small package or a small leak from a large package) First: Isolate in all directions (feet/meters) 600/200 Then: Protect persons downwind (miles/kilometers) Day 0.7/1.1 Night 2.5/4.1 Large spills (From a large package or from many small packages) First: Isolate in all directions (feet/meters) 3000/1000 Then: Protect persons downwind (miles/kilometers) Day 4.7/7.5 Night 7.01 /11.01 DP, when used as a weapon Small spills (From a small package or a small leak from a large package) First: Isolate in all directions (feet/meters) 100/30 Then: Protect persons downwind (miles/kilometers) Day 0.2/0.3 Night 0.5/0.8 Large spills (From a large package or from many small packages) First: Isolate in all directions (feet/meters) 600/200 Then: Protect persons downwind (miles/kilometers) Day 0.7/1.1 Night 1.6/2.5 Phosgene Small spills (From a small package or a small leak from a large package) First: Isolate in all directions (feet/meters) 300/100 Then: Protect persons downwind (miles/kilometers) Day 0.4/0.6 Night 1.6/2.5 Large spills (From a large package or from many small packages) First: Isolate in all directions (feet/meters) 500/150 Then: Protect persons downwind (miles/kilometers) Day 2.0/3.2 Night 6.1/9.7 Diphosgene Small spills (From a small package or a small leak from a large package) First: Isolate in all directions (feet/meters) 100/30 Then: Protect persons downwind (miles/kilometers) Day 0.1/0.2 Night 0.1/0.2 Large spills (From a large package or from many small packages) First: Isolate in all directions (feet/meters) 100/30 Then: Protect persons downwind (miles/kilometers) Day 0.2/0.3 Night 0.3/0.5 Fire Extinguishing: Phosgene may burn, but does not easily ignite. For small fires, use dry chemical or carbon dioxide. Use water spray, fog, or foam for larger fires. Move container from fire area if you can do so without risk. Stay
Phosgene oxime (Agent CX, WMD) away from the ends of tanks and cool exposed containers with water until well after the fire is out. Isolate the area until gas has dispersed. Poisonous gases are produced in fire, including hydrogen chloride, carbon monoxide, and chlorine fumes. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. Do not get water inside containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Diphosgene (DP) will not burn. However, it is possible that a DP tank may be adjacent to a fire. In a fire, a storage tank will heat and the tank may overpressurize and explode, so evacuate the area. When heated, DP breaks down to toxic phosgene, which breaks down into chlorine and hydrogen chloride gases. The danger from a heated DP tank is too great to risk a manned firefighting effort; if possible, an unattended fire monitor aimed at the upper part of the diphosgene tank will cool the tank and may prevent tank failure. In general, it is best to use a spray or fog pattern rather than a solid stream, to avoid spreading the burning fuel around. Disposal Method Suggested: Phosgene may be neutralized by covering it with sodium bicarbonate or an equal mixture of soda ash and slaked lime. After mixing, spray carefully with water. Transfer slowly to a larger container of water. Do not use water directly on spill. Pass controlled discharges of phosgene through 10% NaOH solution in a scrubbing tower.[22] Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant ($100 kg/ mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. References National Institute for Occupational Safety and Health. (1976). Criteria for a Recommended Standard: Occupational Exposure to Phosgene, NIOSH Document No. 76-137 US Environmental Protection Agency. (June 13, 1977). Chemical Hazard Information Profile: Phosgene. Washington, DC Sax, N. I. (Ed.). (1983). Dangerous Properties of Industrial Materials Report, 3, No. 9799 US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Phosgene. Washington, DC: Chemical Emergency Preparedness Program New York State Department of Health. (March 1986). Chemical Fact Sheet: Phosgene. Albany, NY: Bureau of Toxic Substance Assessment
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New Jersey Department of Health and Senior Services. (April 2004). Hazardous Substances Fact Sheet: Phosgene. Trenton, NJ Schneider, A. L., et al. (2007). CHRIS 1 CD-ROM Version 2.0, United Coast Guard Chemical Hazard Response Information System (COMDTINST 16465.12C). Washington, DC: United States Coast Guard and the Department of Homeland Security The Riegle Report: A Report of Chairman Donald W. Riegle, Jr. and Ranking Member Alfonse M. D’Amato of the Committee on Banking, Housing and Urban Affairs with Respect to Export Administration, United States Senate, 103rd Congress, 2d Session, (May 25, 1994) Besch, T., Moss, C., the Battlebook Project Team, et al. (1991). MEDICAL NBC Battlebook (304 p), Tech Guide 244. Ft. Leonard Wood, MO: The US Army Center for Health Promotion and Preventive Medicine (USACHPPM)
Phosgene oxime (Agent CX, WMD) P:0555 Molecular Formula: CHCl2NO Synonyms: Carbonyl chloride oxime; CX; Dichlorformaldehyde-oxime; Dichloroformaldoxime; 1,2Dichloroformoxime; Dichloroformoxime; Dichlormethylenhydroxylamine; Dichloroximinomethane; Kohlensauredichloridoxime (German) CAS Registry Number: 1794-86-1 RTECS® Number: Not established UN/NA & ERG Number: 2811/154 Regulatory Authority and Advisory Bodies Report any release of WMD to National Response Center 1-800-424-8802. While not a mandated “Federally listed” waste, CX is more toxic than most RCRA listed chemicals. However, GF is a “listed” hazardous waste in some states where it may have been stockpiled by the military. WGK (German Aquatic Class): No value assigned. Description: Phosgene oxime (military designation CX) is a noncombustible urticant (nettle agent, blister agent) with a short (seconds to minutes) latency period. CX is a colorless, low-melting point (crystalline, white powder) solid or as a liquid (liquid above 39 C; solid below 35 C). On hot days (or at body temperature) it can appear as a yellowish-brown liquid. It has a high vapor pressure (the vapor pressure of the solid is high enough to produce symptoms), slowly decomposes at normal temperatures. It has an intense, disagreeable, penetrating, and violently irritating, peppery odor. Odor detectable at less than 0.3 ppm. Molecular weight 5 113.93 Da; Freezing/Melting point 5 3540 C; boiling point 5 129 C (with decomposition); Vapor density 5 3.9; Vapor pressure 5 11.2 mmHg at 20 C (solid); 13 mmHg at 40 C (liquid); Volatility 5 1800 mg/m3 at
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Phosgene oxime (Agent CX, WMD)
20 C; 76,000 mg/m3 at 40 C; Latent heat of vaporization 5 101 cal/g at 40 C; Decomposition temperature 5 ,128 C. Solubility in water 5 dissolves slowly and completely. High solubility in organic solvents. History of the chemical: CX was invented in Germany in 1929; it is among the least well-studied chemical warfare agents; therefore, detailed information is limited. Although it is believed that CX was never used on the battlefield, it was after WW II that the military tested concentrated phosgene oxime. These tests revealed that CX was a highly effective and painful chemical warfare agent. Phosgene oxime is of military interest because it easily penetrates garments and rubber much more quickly than do other chemical agents. It is possible that Iraq used CX in the IranIraq war, and North Korea may have produced and stocked quantities of this chemical agent. Phosgene oxime (CX) gives off dangerous gas. It does take very little of this gas to damage a victim’s lungs. Terrorists might put CX in an exploding bomb in order to break up the solid into an aerosol that can penetrate the skin and lungs. Once exposed, the victim feels immediate pain and the need to escape. Phosgene oxime (CX) easily penetrates fabrics and rubbers and cause great pain and skin damage (without blisters) in less than a minute. Soon after contact the skin dies. Recovery may take up to 6 months. Eye contact can cause blindness. Inhalation attacks the lungs, resulting in damage that can be permanent. Potential Exposure: There is no industrial use for Phosgene oxime (CX) and because of its extreme instability, the pure material is not likely to be used in military operations.[FM 3-9] CX is especially dangerous when mixed with other chemicals such as nerve agents. It burns away the skin making it more permeable to any other “added” agents. No other chemical agent is capable of producing immediate extreme pain followed by rapid local tissue death (necrosis). Post World War II studies indicate that concentrations below 8% cause no or inconsistent effects.[ATSDR] Persistence of Chemical Agent: Soil: about 2 h. Material surfaces and water: relatively nonpersistent. Incompatibilities: Phosgene oxime (CX) is among the most important halogenated oximes. CX reacts with water, sweat, and heat, forming hydrochloric acid. CX may be an oxidizer, and it may ignite combustibles (e.g., wood, paper, oil, or clothing). CX is incompatible with strong acids and bases; hydrides and other strong reducing agents; strong oxidizing acids, peroxides, and hydroperoxides. Not hydrolyzed by dilute acids; reacts violently in basic solutions forming carbon dioxide, hydrogen chloride, and hydroxylamine. Hydrolysis products include HCl and methylarsenic oxide. CX quickly penetrates rubber and clothing. CX decomposes when in contact with many metals; it is corrosive to most metals, and contact with metals may cause the release flammable hydrogen gas. Traces of many metals cause it to decompose; however, it corrodes most metals. Permissible Exposure Limits in Air: Conversion factor 5 1 ppm 5 4.66 mg/m3 at 77 C.
The immediately dangerous to life and health (IDLH) concentration of CX has not been defined. Protective Action Criteria (PAC) CG* TEEL-0: 0.0075 mg/m3 PAC-1: 0.028 mg/m3 PAC-2: 0.083 mg/m3 PAC-3: 13 mg/m3 *AEGLs (Acute Emergency Guideline Levels) & ERPGs (Emergency Response Planning Guideline) are in bold face. Determination in Air: According to the USAMRICD, do NOT depend on the following for the detection of Agent CX: M272 water testing kit, MINICAMS, ICAD, M21 remote sensing alarm, CAM, ACAMS, DAAMS, and M8A1 automatic chemical-agent detector alarm are incapable of detecting CX. Likewise, M8 and M9 paper should not be depended upon to detect Agent CX. The M256A1 detector ticket reacts to the presence of CX, but the detection threshold is not known with certainty. Liquid detection: The portable M256A1 has a response time of up to 15 min. The following detectors are listed for Agent CX detection in the Guide for the Selection of Chemical Detection Equipment for Emergency First Responders, 3rd Edition, published by the US Department of Homeland Security: Chemical Agent Detector C2 Kit (021330) for vapor, liquids, aerosols: Start-up time (based on experience) 15 min; response time (regardless of experience) 2025 min (Anachemia Canada, Inc.); and M256A1 (T503) (063230COM) Chemical Agent Detector Simulator Training Kits for vapor only: Start-up time (based on experience) 15 min; response time (regardless of experience) 2025 min (Anachemia Canada, Inc.) The following detectors have the capacity to detect CX at the threshold limits given[USAMRICD]: Liquid: M18A2 0.5 mg/min3 Air: M90 (M90-D1-C) 0.15 mg/min3 M93A1 Fox 10100 μg/L Permissible Concentration in Water: Do NOT use the M272 water testing kit.[USAMRICD] Determination in Water: Contact pollution control authorities and advise shutting water intakes. CX dissolves in water and breaks down into toxic products that are much less dangerous than phosgene oxime, but still poisonous. Do not allow people to drink water containing even the breakdown products. Routes of Entry: Skin, eye contact, inhalation. Harmful Effects and Symptoms Phosgene oxime (CX) is a rapid-acting casualty agent. The effects of phosgene oxime vapor and liquid on the skin, eyes, and lungs are almost instantaneous, causing immediate pain upon contact with the liquid and when the vapors are inhaled. Little is known about how CX works but it eats its way through protective clothing, the skin, and eventually reaches the blood. Phosgene oxime (CX) will cause blindness, kill skin horribly, and with enough of it on the skin a
Phosgene oxime (Agent CX, WMD) victim could die. Eyes: The eyes will immediately burn, the eyelids will swell, and the victim’s cornea will scar, causing permanent damage to the eyes with possible blindness. Lungs: The effects are immediate: The victim will sneeze and cough, with runny nose. The lungs will fill with fluid causing pulmonary edema, a medical emergency that can be delayed for several hours. This can cause death. Skin: Immediate stinging pain will be felt. The skin reddens and will eventually blister (up to 12 h after exposure). Ingestion: It is difficult to understand how one might swallow Phosgene oxime (CX), but it possibly may happen. Animal studies show that the victim’s stomach and intestines would swell and bleed. Short Term Exposure: Pain and local tissue destruction occur immediately on contact with skin, eyes, and mucous membranes. Phosgene oxime is rapidly absorbed from the skin and eyes and may result in systemic toxicity. Phosgene oxime causes redness, wheals (hives), and urticaria on the skin, but does not produce a fluid-filled blister (vesication). Despite the lack of initial blister formation, phosgene oxime produces more tissue damage than the blister agents. Known as a “nettle gas,” CX produces immediate pain varying from a mild prickling to almost intolerable pain similar to a severe bee sting. Phosgene oxime has no antidote. Treatment is similar to that of the mustard agents. It causes violent irritation to the mucous membranes of the nose and eyes. Even at low temperature it has sufficient vapor pressure to produce tearing. When CX comes in contact to the skin, the area turns pale in 30 s and develops a red ring around the area. A wheal forms in about 30 min; the blanched area turns brown in 24 h and a scab forms in about a week. The scab usually falls off in about 3 weeks. Itching may be present throughout healing, which in some cases may be delayed beyond 2 months.[Army FM 3-9 and CDC] The LD50 for skin exposure is estimated as 25 mg/kg. LCt50 5 no accurate data available; the estimated LCt50 by inhalation is 15002000 mg-min/m3; ICt50 (respiratory) 25 mg-min/m3. Inhaled phosgene oxime is extremely irritating to the upper airways and causes pulmonary edema. Irritation occurs with exposures to 0.2 mg-min/m3 and becomes unbearable at 3 mg-min/m3 . The estimated LCt50 (the product of concentration times time that is lethal to 50% of the exposed population by inhalation) is 1500 to 2000 mg-min/m3 .[ATSDR] Long Term Exposure: May cause permanent injury, including lung damage and blindness. Information is unavailable about the carcinogenicity, developmental toxicity, or reproductive toxicity from chronic or repeated exposure to phosgene oxime. Points of Attack: Skin, mucous membranes of the nose and eyes. Medical Surveillance: There are no specific tests to confirm exposure. Extreme pain may persist for days. Patients/ victims should be observed for signs of whole-body (systemic) toxicity, including accumulation of fluid in the lungs (pulmonary edema). Gastric lavage is contraindicated
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following ingestion of this agent due to the risk of perforation of the esophagus or upper airway.[NIOSH] First Aid: A note to first responders: You cannot help the victim if you kill yourself. Do not enter an area contaminated with either CX vapor or liquid unprotected. The only option to your own survival is by wearing “Level A” protection. You must act quickly. Remove the victim to fresh air without exposing yourself— do not touch the victim! Only when the victim is outside the hot and warm zones and decontaminated you can help. If breathing is difficult, give oxygen. Do not make the victim vomit if the victim has swallowed Phosgene oxime. If the victim is conscious, give the victim milk. Get the victim to a doctor or medical facility as soon as possible, even if symptoms do not appear serious; symptoms are often delayed. Decontamination: Note to first responders: Depending on the dose and the equipment available to you: Evacuate the area and shut down heating, ventilation, and air conditioning systems to prevent further spread of Phosgene oxime (CX). Call for medical and hazmat assistance immediately. If you get CX on yourself, decontaminate immediately. Even if you think you are not contaminated, be sure to thoroughly shower and change clothes as soon as you can after the incident. Because of the rapid reaction of CX with the skin, decontamination may not be entirely effective once pain occurs. Nevertheless, decontaminate as rapidly as possible by flushing the area with large amounts of water to remove any agent that has not reacted with the skin. Wash the victim with warm water and soap. Bleach does not work with CX. Be certain you have decontaminated the victims as much as you can before they leave the area so that they do not spread the Phosgene oxime (CX). Personal Protective Methods: Use Level A protection. CX quickly penetrates rubber and clothing. Corrosive to most metals. Respirator Selection: CX quickly penetrates rubber and clothing. Corrosive to most metals. Storage: Stable in steel containers. Shipping: Shipping Name: Toxic solids, organic, n.o.s. Hazardous Class or Division: 6.1. Subsidiary Hazardous Class or Division: Label Poison (Toxic). Packing Group III. Spill Handling: Immediately evacuate everyone, including yourself. Immediately call for medical and hazmat assistance. Notify police, federal authorities, medical, hazmat, and emergency authorities. Immediately decontaminate victim. Do not touch the victim or allow Phosgene oxime (CX) to touch your skin or eyes. If possible, ventilate the area. If response personnel must walk through the spilled agent, wear the appropriate Level A protection. Keep combustibles (e.g., wood, paper, and oil) away from the spilled agent. Use water spray to reduce aerosols or divert aerosol cloud drift. Avoid allowing water runoff to contact the spilled agent. Do not direct water at the spill or the source of the leak. Stop the leak if it is possible to do so without risk to personnel. Prevent entry into waterways, sewers, basements,
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Phosmet
or confined areas. Isolate the area until aerosol has dispersed.[NIOSH] Initial isolation and protective action distances Distances shown are likely to be affected during the first 30 min after materials are spilled and could increase with time. If more than one tank car, cargo tank, portable tank, or large cylinder involved in the incident is leaking, the protective action distance may need to be increased. You may need to seek emergency information from CHEMTREC at (800) 424-9300 or seek professional environmental engineering assistance from the US EPA Environmental Response Team at (908) 548-8730 (24-h response line). If a tank, rail car, or tank truck is involved in a fire, isolate it for 0.5 mile (800 m) in all directions; also, consider initial evacuation for 0.5 mile (800 m) in all directions. CX, when used as a weapon Small spills [involving the release of approximately 52.83 gallons (200 L) or less] First: Isolate in all directions (feet/meters) 100/30 Then: Protect persons downwind (miles/kilometers) Day 0.1/0.2 Night 0.3/0.5 Large spills [involving quantities greater than 52.83 gallons (200 L)] First: Isolate in all directions (feet/meters) 300/90 Then: Protect persons downwind (miles/kilometers) Day 0.6/1.0 Night 1.9/3.1 Fire Extinguishing: Phosgene oxime (CX) is noncombustible; it burns weakly, if at all. CX may decompose upon heating producing corrosive and/or toxic gases. Containers may explode when heated. In case of fire, evacuate the area, including yourself. CX may be an oxidizer, and it may ignite combustible materials (e.g., wood, paper, oil, or clothing). If there is some reason that you have to put out the fire—for example, there are things nearby that cannot be allowed to burn—use unattended equipment, then evacuate everyone immediately, including yourself. If you must extinguish a Phosgene oxime (CX) fire, use water streams, water fog, alcohol foam, universal foam, and, for confined fires, carbon dioxide. (For small fires, use dry chemical, carbon dioxide, or water spray. For large fires, use dry chemical, carbon dioxide, alcohol-resistant foam, or water spray.) Vapors are heavier than air and will collect in low areas. Keep out of these areas; stay upwind. Hazardous concentrations may spread along the ground and collect and stay in poorly ventilated, low-lying, or confined areas (e.g., sewers, basements, and tanks). If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. Move containers from the fire area if it is possible to do so without risk to personnel. Dike fire control water for later disposal; do not scatter the material. For fire involving tanks or car/trailer loads, fight the fire from maximum distance or use unmanned hose holders or monitor nozzles. Do not get water inside
containers. Cool containers with flooding quantities of water until well after fire is out. Withdraw immediately in case of rising sound from venting safety devices or discoloration of tanks. Always stay away from tanks engulfed in fire. Run-off from fire control or dilution water may be corrosive and/or toxic, and it may cause pollution. If the situation allows, control and properly dispose of run-off (effluent). Disposal Method Suggested: Seek expert advice from armed services (see Reference section), Center for Disease Control headquarters in Atlanta, GA. References US Army Field Manual (DA FM) 3-9 (PCN 320 008457 00); US Navy Publication No P-467; US Air Force Manual No 355-7; Potential Military Chemical/Biological Agents and Compounds. Washington, DC: Headquarters, Department of the Army, Headquarters, Department of the Navy, Headquarters, Department of the Air Force, December 1990 Sidell, R. (1997). Medical Aspects of Chemical and Biological Warfare, Borden Institute, Walter Reed Army Medical Center, Washington, DC; Office of The Surgeon General, United States Army, Falls Church, Virginia; United States Army Medical Department Center and School, Fort Sam Houston, Texas; United States Army Medical Research and Materiel Command, Fort Detrick, Frederick, Maryland, Uniformed Services University of the Health Sciences, Bethesda, MD[MACBW] CDC/NIOSH, The Emergency Response Safety and Health Database, ,http://www.cdc.gov/NIOSH/ershdb/ EmergencyResponseCard_29750015.html. Fatha, A. A., Arcilesi, R. D., Peterson, J. C., Lattin, C. H., Well, C. Y., & McClintock, J. A. (January 2007). Guide for the Selection of Chemical Detection Equipment for Emergency First Responders, 3rd Edition, Guide 100-6. Washington, DC: US Department of Homeland Security
Phosmet
P:0560
Molecular Formula: C11H12NO4PS2 Synonyms: APPA; Decemthion; Decemthion P-6; O, O-Dimethyl phthalimidiomethyl dithiophosphate; O,ODimethyl S-(N-phthalimidomethyl) dithiophosphate; O, O-Dimethyl S-phthalimidomethyl phosphorodithioate; ENT25,705; Fosmet (Spanish); Ftalophos; Imidan; Kemolate; N-(Mercaptomethyl)phthalimide S-(O,Odimethyl phosphorodithioate); Percolate; Phosphorodithioic acid, S-[(1,3-dihydro-1,3-dioxo-isoindol-2-yl)methyl] O,Odimethyl ester; Phosphorodithioic acid, O,O-dimethyl ester, S-ester with N-(mercaptomethyl) phthalimide; Phthalimide, N-(mercaptomethyl)-, S-ester with O,O-dimethyl phosphorodithioate; Phthalimido-O,O-dimethyl phosphorodithioate; Phthalimidomethyl O,O-dimethyl phosphorodithioate; Phthalophos; PMP; Prolate; R 1504; Smidan; Stauffer R 1504
Phosmet CAS Registry Number: 732-11-6 RTECS® Number: TE2275000 UN/NA & ERG Number: UN2783 (organophosphorus pesticides, solid, toxic)/152 EC Number: 211-987-4 [Annex I Index No.: 015-101-00-5] Regulatory Authority and Advisory Bodies US EPA, FIFRA, 1998 Status of Pesticides: Supported. Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 10/10,000 lb (4.54/4540 kg). Reportable Quantity (RQ): 1 lb (0.454 kg). US DOT MARINE POLLUTANT (49CFR, Subchapter 172.101, Appendix B). US DOT 49CFR172.101, Inhalation Hazard Chemical as organophosphates. European/International Regulations (not listed in Annex I, but the following may apply): Hazard Symbol: T1, N; Risk phrases: R27/28; R50/53; Safety phrases: S1/2; S28; S36/ 37; S45; S60; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): No value assigned. Description: Phosmet is a white crystalline solid. Molecular weight 5 317.33; Boiling point 5 (decomposes below BP) .100 C; Freezing/Melting point 5 72 C. Hazard; Vapor pressure 5 4.9 3 10 2 7 mbar at 20 C. Identification (based on NFPA-704 M Rating System): Health 3, Flammability 1, Reactivity 2. Slightly soluble in water. Potential Exposure: Compound Description: Agricultural Chemical; Mutagen; Reproductive Effector; Human Data. Used as an organophosphorus insecticide and acaricide. Incompatibilities: Not compatible with other pesticides under alkaline conditions. Contact with water, steam, or moisture forms phthalic acids. Slightly corrosive to metals in the presence of moisture. Permissible Exposure Limits in Air Protective Action Criteria (PAC) TEEL-0: 0.025 mg/m3 PAC-1: 0.075 mg/m3 PAC-2: 0.54 mg/m3 PAC-3: 40 mg/m3 Russia has set a ceiling value of 0.3 mg/m3 in work-place air. Russia has also set a MAC of 0.009 mg/m3 in ambient air in residential area on a once-daily basis and 0.004 mg/ m3 on a daily average basis. Determination in Air: NIOSH Analytical Method (IV) Method #5600, Organophosphorus pesticides. Permissible Concentration in Water: Russia[36] set a MAC of 0.2 mg/L in surface water. Determination in Water: Fish Tox: 4.41815000 ppb MATC (HIGH). Octanolwater coefficient: Log Kow 5 2.8. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Absorbed by the skin. Harmful Effects and Symptoms Short Term Exposure: Irritates the eyes and skin on contact. This material is a highly toxic organophosphate; the probable oral lethal dose for humans is 50500 mg/kg or
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between 1 teaspoon and 1 oz for a 150-lb person. It is a cholinesterase inhibitor and has central nervous system effects. Oral lethal doses in humans have been reported at 50 mg/kg. Acute exposure to phosmet may produce the following signs and symptoms: pinpoint pupils, blurred vision, headache, dizziness, muscle spasms, and profound weakness. Vomiting, diarrhea, abdominal pain, seizures, and coma may also occur. The heart rate may decrease following oral exposure or increase following dermal exposure. Chest pain may be noted. Hypotension (low blood pressure) may occur, although hypertension (high blood pressure) is not uncommon. Dyspnea (shortness of breath) may be followed by respiratory collapse. Giddiness is common. Long Term Exposure: Cholinesterase inhibitor; cumulative effect is possible. This chemical may damage the nervous system with repeated exposure, resulting in convulsions, respiratory failure. May cause liver damage. Human Tox 5 7.00000 ppm Health Advisory (HIGH). Points of Attack: Respiratory system, lungs, central nervous system, cardiovascular system, skin, eyes, plasma and red blood cell cholinesterase. Medical Surveillance: Before employment and at regular times after that, the following are recommended: plasma and red blood cell cholinesterase levels (tests for the enzyme poisoned by this chemical). If exposure stops, plasma levels return to normal in 12 weeks while red blood cell levels may be reduced for 13 months. When cholinesterase enzyme levels are reduced by 25% or more below preemployment levels, risk of poisoning is increased, even if results are in lower ranges of “normal.” Reassignment to work not involving organophosphate or carbamate pesticides is recommended until enzyme levels recover. If symptoms develop or overexposure occurs, repeat the above tests as soon as possible and get an examination of the nervous system. Also consider complete blood count. Consider chest X-ray following acute overexposure. Liver function tests. Do not drink any alcoholic beverages before or during use. Alcohol promotes absorption of organic phosphates. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Speed in removing material from skin is of extreme importance. Shampoo hair promptly if contaminated. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and/or slurry of activated charcoal in water; and induce vomiting. Do not make an unconscious person vomit. Obtain authorization and/or further instructions from the local hospital for
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administration of an antidote or performance of other invasive procedures. Transport to a health-care facility. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuous-flow mode; or use a NIOSH/MSHA- or European Standard EN149approved self-contained breathing apparatus with a full facepiece operated in pressure-demand or other positive-pressure mode. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, well-ventilated area away from other pesticide, alkaline conditions, water, and other forms of moisture. Where possible, automatically transfer material from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of this chemical should be grounded and bonded. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: Organophosphorus pesticides, solid, toxic, require a shipping label of “POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 6.1 and Packing Group III. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. As for other organophosphorus pesticides stay upwind; keep out of low areas. Ventilate closed spaces before entering them. Remove and isolate contaminated clothing at the site. Do not touch spilled material. Use water spray to reduce vapors. Take up small spills with sand or other noncombustible absorbent material and place in containers for later disposal. Take up small, dry spills with clean shovel and place in clean, dry container. Dike far ahead of large spills for later disposal. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste.
If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This material may burn but does not ignite readily. For small fires, use dry chemical, carbon dioxide, water spray, or foam. For large fires, use water spray, fog, or foam. Stay upwind; keep out of low areas. Move container from fire area if you can do it without risk. Fight fire from maximum distance. Dike fire control water for later disposal; do not scatter material. Wear positive pressure breathing apparatus and special protective clothing. Poisonous gases are produced in fire, including nitrogen oxides, phosphorous oxides, and sulfur oxides. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. Containers may explode in fire. From a secure, explosionproof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant ($100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. In accordance with 40CFR165, follow recommendations for the disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by contacting your local or federal environmental control agency or by contacting your regional EPA office. Small amounts may be decomposed with hypochlorite. For large amounts, incineration with effective gas scrubbing is recommended.[22] References US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Phosmet. Washington, DC: Chemical Emergency Preparedness Program New Jersey Department of Health and Senior Services. (March 1999). Hazardous Substances Fact Sheet: Decemthion. Trenton, NJ
Phosphamidon
P:0570
Molecular Formula: C10H19ClNO5P Common Formula: (CH3O)2POOC(CH3)QC(Cl)CON (CH2CH3)2
Phosphamidon Synonyms: Apamidon; C 570; C-570; (2-Chlor-3-diaethylamino-methyl-3-oxo-prop-1-en-yl)-dimethylphosphat (German); 2-Chloro-3-(diethylamino)-1-methyl-3-oxo-1-propenyldimethyl phosphate; 2-Chloro-2-diethylcarbamoyl-1methylvinyl dimethyl phosphate; 1-Chloro-diethylcarbamoyl-1-propen-2-yl dimethyl phosphate; Ciba 570; Crophosphate; Dimecron; Dimecron 100; O,O-Dimethyl O-[2-chloro-2-(N,N-diethylcarbamoyl)-1-methylvinyl] phosphate; Dimethyl 2-chloro-2-diethylcarbamoyl-1-methylvinylphosphate; Dimethyl diethylamido-1-chlorocrotonyl(2) phosphate; O,O-Dimethyl-O-(1-methyl-2-chlor-2-N, N-diethyl-carbamoyl)-vinyl-phosphat (German); [O,ODimethyl O-[1-methyl-(2-chloro-2-diethylcarbamoyl)vinyl] phosphate; Dimethyl phosphate of 2-chloro-N,N-diethyl-3hydroxycrotonamide; Dimethyl phosphate ester with 2chloro-N,N-diethyl-3-hydroxycrotonamide; Dimonex; Dixon; ENT25,515; Fosfamidon (Spanish); Fosfamidone; Foszfamidon; ML 97; Merkon phosphamidone; NCIC00588; OMS 1325; OR1191; Phosphamidon; Phosphate de dimethyle et de(2-chloro-2-diethylcarbamoyl-1-methylvinyle) (French); Phosphoric acid, 2-chloro-3-(diethylamino)-1-methyl-3-oxo-1-propenyl dimethyl ester; Phosphoric acid, dimethyl ester, with 2-chloro-N,N-diethyl-3hydroxycrotonamide CAS Registry Number: 13171-21-6; 23783-98-4 [(Z) isomer)]; 297-99-4 [(E) isomer] RTECS® Number: TC2800000 UN/NA & ERG Number: UN3018 (organophosphorus pesticide, liquid, toxic)/152 EC Number: 236-116-5 [Annex I Index No.: 015-022-00-6] (phosphamidon) Regulatory Authority and Advisory Bodies Carcinogenicity: NCI: Carcinogenesis Bioassay (feed); equivocal evidence: rat; no evidence: mouse. US EPA, FIFRA 1998 Status of Pesticides: Canceled. Very Toxic Substance (World Bank).[15] Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 100 lb (45.4 kg). Reportable Quantity (RQ): 100 lb (45.4 kg). US DOT Regulated Marine Pollutant (49CFR172.101, Appendix B), severe pollutant. US DOT 49CFR172.101, Inhalation Hazard Chemical as organophosphates. Rotterdam Convention Annex III [Chemicals Subject to the Prior Informed Consent Procedure (PIC)] (soluble liquid formulations of the substance that exceeds 1000 g active ingredient). European/International Regulations: Hazard Symbol: T 1 , N; Risk phrases: R24; R28; R50/53; R68; Safety phrases: S1/2; S23; S36/37; S45-S60; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): 3—Highly water polluting (CAS: 13171-21-6). Description: Phosphamidon is a pale yellow oily liquid. Molecular weight 5 299.72; Specific gravity (H2O:1) 5 1.22; Boiling point 5 162 C at 1.5 mmHg; Freezing/ Melting point 5 45 C. Hazard Identification (based on
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NFPA-704 M Rating System): Health 3, Flammability 1, Reactivity 0. Soluble in water. Potential Exposure: Compound Description: Agricultural Chemical; Tumorigen, Mutagen; Reproductive Effector. This material is used as an insecticide on citrus, cotton, and deciduous fruit and nuts. It is also an acaricide. Incompatibilities: Strong oxidizers may cause release of toxic phosphorus oxides. Organophosphates, in the presence of strong reducing agents such as hydrides, may form highly toxic and flammable phosphine gas. Keep away from alkaline materials. Attacks metals, such as aluminum, iron, tin. Permissible Exposure Limits in Air Protective Action Criteria (PAC) TEEL-0: 0.06 mg/m3 PAC-1: 0.15 mg/m3 PAC-2: 0.3 mg/m3 PAC-3: 60 mg/m3 Determination in Water: Fish Tox 5 1445.67277000 ppb (EXTRA LOW); FISH STV (Sediment Toxicity Value): LOW; Octanolwater coefficient: Log Kow 5 ,0.9. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Irritates the eyes. May affect the nervous system, causing convulsions, respiratory failure, and death. Higher exposures can cause pulmonary edema, a medical emergency that can be delayed for several hours. This can cause death. This material is extremely toxic; the probable oral lethal dose for humans is 550 mg/kg or between 7 drops and 1 teaspoonful for a 150-lb person. It is a cholinesterase inhibitor. Acute exposure to phosphamidon may produce pinpoint pupils, blurred vision, headache, dizziness, muscle spasms, and profound weakness. Vomiting, diarrhea, abdominal pain, seizures, and coma may also occur. The heart rate may decrease following oral exposure or increase following dermal exposure. Hypotension (low blood pressure) may occur, although hypertension (high blood pressure) is not uncommon. Chest pain may be noted. Respiratory effects include dyspnea (shortness of breath), respiratory depression, and respiratory paralysis. Psychosis may occur. Long Term Exposure: Cholinesterase inhibitor; cumulative effect is possible. This chemical may damage the nervous system with repeated exposure, resulting in convulsions, respiratory failure. May cause liver damage. Human Tox 5 0.14000 ppm (EXTRA HIGH). Points of Attack: Respiratory system, lungs, central nervous system, cardiovascular system, skin, eyes, plasma and red blood cell cholinesterase. Medical Surveillance: Before employment and at regular times after that, the following are recommended: plasma and red blood cell cholinesterase levels (tests for the enzyme poisoned by this chemical). If exposure stops, plasma levels return to normal in 12 weeks while red blood cell levels may be reduced for 13 months.
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Phosphamidon
When cholinesterase enzyme levels are reduced by 25% or more below preemployment levels, risk of poisoning is increased, even if results are in lower ranges of “normal.” Reassignment to work not involving organophosphate or carbamate pesticides is recommended until enzyme levels recover. If symptoms develop or overexposure occurs, repeat the above tests as soon as possible and get an examination of the nervous system. Also consider complete blood count. Consider chest X-ray following acute overexposure. Do not drink any alcoholic beverages before or during use. Alcohol promotes absorption of organic phosphates. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Speed in removing material from skin is of extreme importance. Shampoo hair promptly if contaminated. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Obtain authorization and/or further instructions from the local hospital for administration of an antidote or performance of other invasive procedures. Transport to a healthcare facility. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in pressure-demand or other positive-pressure mode.
Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, wellventilated area away from alkalis. Shipping: This compound requires a shipping label of “POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 6.1 and Packing Group II. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Stay upwind; keep out of low areas. Ventilate closed spaces before entering them. Do not touch spilled material; stop leak if you can do so without risk. Use water spray to reduce vapors. Small spills: absorb with sand or other noncombustible absorbent material and place into containers for later disposal. Large spills: dike far ahead of spill for later disposal. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This material may burn, but does not ignite readily. For small fires, use dry chemical, carbon dioxide, water spray, or foam. For large fires: use water spray, fog, or foam. Stay upwind; keep out of low areas. Move containers from fire area if you can do it without risk. Fight fire from maximum distance. Dike fire control water for later disposal; do not scatter the material. Poisonous gases, including phosphorous oxides, hydrogen chloride, and nitrogen oxides, are produced in fire. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Small quantities may be treated with alkali followed by landfill disposal. Large quantities should be incinerated with effluent gas scrubbing.[22] In accordance with 40CFR165, follow recommendations for the disposal of pesticides and pesticide containers. Must be
Phosphine disposed properly by following package label directions or by contacting your local or federal environmental control agency or by contacting your regional EPA office. References US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Phosphamidon. Washington, DC: Chemical Emergency Preparedness Program New Jersey Department of Health and Senior Services. (September 1999). Hazardous Substances Fact Sheet: Phosphamidon. Trenton, NJ
Phosphine
P:0580
Molecular Formula: H3P Common Formula: PH3 Synonyms: Celphos; Delicia; Detia gas-EX-B; Fosfamia (Spanish); Hydrogen phosphide; Phosphorous trihydride; Phosphorous hydride; Phosphorated hydrogen; Phosphorwasserstoff (German); Phostoxin CAS Registry Number: 7803-51-2 RTECS® Number: SY7525000 UN/NA & ERG Number: UN2199/119 EC Number: 232-260-8 [Annex I Index No.: 015-181-00-1] Regulatory Authority and Advisory Bodies Department of Homeland Security Screening Threshold Quantity (pounds): Release hazard 10,000 ($1.00% concentration). (1% concentration; Theft hazard 15 ($0.67% concentration). Department of Homeland Security Screening Threshold Quantity (pounds): Sabotage/Contamination Hazard: A placarded amount (commercial grade). Carcinogenicity: EPA: Not Classifiable as to human carcinogenicity. Banned or Severely Restricted (several countries) (UN).[13] Very Toxic Substance (World Bank).[15] Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Clean Air Act: Hazardous Air Pollutants (Title I, Part A, Section 112); Accidental Release Prevention/Flammable Substances, (Section 112[r], Table 3), TQ 5 5000 lb (2270 kg). US EPA Hazardous Waste Number (RCRA No.): P096. RCRA, 40CFR261, Appendix 8 Hazardous Constituents. Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 500 lb (227 kg). Reportable Quantity (RQ): 100 lb (45.4 kg). EPCRA Section 313 Form R de minimis concentration reporting level: 1.0%. US DOT 49CFR172.101, Inhalation Hazardous Chemical. European/International Regulations: Hazard Symbol: F, T, N; Risk phrases: R12; R17; R26; R34; R50; Safety phrases: S1/2; S28; S36/37; S45; S61; S63 (see Appendix 4). WGK (German Aquatic Hazard Class): 2—Hazard to waters.
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Description: Phosphine is a colorless gas that is shipped as liquefied compressed gas. Odorless when pure, it has the odor of garlic or the foul odor of decaying fish. The level at which humans detect the odor of phosphine (odor threshold) does not provide sufficient warning of dangerous concentrations. Phosphine presents an additional hazard in that it ignites at very low temperatures. Shipped as a liquefied compressed gas. The pure compound is odorless. The odor threshold is 0.14 ppm. Molecular weight 5 34.00; Specific gravity (H2O:1) 5 0.8; Boiling point 5 88 C; Freezing/Melting point 5 133 C; Relative vapor density (air 5 1): 1.18; Vapor pressure 5 41.3 atm; .760 mmHg at 20 C; Flash point 5 (flammable gas) 104 C; Autoignition temperature (depends on concentration and diluent) 5 38100 C. Explosive limits: LEL 5 1.8%; UEL 5 unknown. Hazard Identification (based on NFPA-704 M Rating System): Health 4, Flammability 4, Reactivity 2. Slightly soluble in water; solubility 5 25 mL/100 mL at 17 C. Potential Exposure: Compound Description: Agricultural Chemical; Mutagen; Human Data. Phosphine is used as a fumigant; in the semiconductor industry, as a doping agent for electronic components (to introduce phosphorus into silicon crystals); in chemical synthesis; used as a polymerization initiator; as an intermediate for some flame retardants. Also, exposures may occur when acid or water comes in contact with metallic phosphides (aluminum phosphide, calcium phosphide). These two phosphides are used as insecticides or rodenticides for grain, and phosphine is generated during grain fumigation. When phosphine toxicity is suspected, but phosphine exposure is not obvious, one should suspect transdermal contamination and/or ingestion of phosphides. Phosphine may also evolve during the generation of acetylene from impure calcium carbide, as well as during metal shaving; sulfuric acid tank cleaning; rustproofing, ferrosilicon, phosphoric acid; and yellow phosphorus explosive handling. Incompatibilities: Phosphine reacts with acids, air, copper, moisture, oxidizers, oxygen, chlorine, nitrogen oxides, metal nitrates, halogens, halogenated hydrocarbons, copper, and many other substances, causing fire and explosion hazard. Extremely explosive; may ignite spontaneously on contact with air at or about 100 C. Attacks many metals. Permissible Exposure Limits in Air Conversion factor: 1 ppm 5 1.39 mg/m3 at 25 C & 1 atm. OSHA PEL: 0.3 ppm/0.4 mg/m3 TWA. NIOSH REL: 0.3 ppm/0.4 mg/m3 TWA; 1 ppm/1 mg/m3 STEL. ACGIH TLV®[1]: 0.3 ppm/0.42 mg/m3 TWA; 1 ppm/ 1.4 mg/m3 STEL. NIOSH IDLH: 50 ppm. Protective Action Criteria (PAC) Phosphine* TEEL-0: 0.3 ppm PAC-1: 1 ppm PAC-2: 2.0 ppm PAC-3: 3.6 ppm
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Phosphine
*AEGLs (Acute Emergency Guideline Levels) & ERPGs (Emergency Response Planning Guideline) are in bold face. Emergency Response Planning Guidelines (AIHA) ERPG-1: Inappropriate ERPG-2: 0.5 ppm ERPG-3: 3.5 ppm DFG MAK: 0.1 ppm/0.14 mg/m3 TWA; Peak Limitation Category II(2); Pregnancy Risk Group C. Arab Republic of Egypt: TWA 0.3 ppm (0.4 mg/m3), 1993; Australia: TWA 0.3 ppm (0.4 mg/m3); STEL 1 ppm (1 mg/ m3), 1993; Austria: MAK 0.1 ppm (0.15 mg/m3), 1999; Belgium: TWA 0.3 ppm (0.42 mg/m3); STEL 1 ppm (1.4 mg/m3), 1993; Denmark: TWA 0.1 ppm (0.15 mg/m3), 1999; Finland: TWA 0.1 ppm (0.15 mg/m3); STEL 0.3 ppm (0.4 mg/m3), 1999; France: VME 0.1 ppm (0.13 mg/m3), VLE 0.3 ppm (0.4 mg/m3), 1999; the Netherlands: MACTGG 0.4 mg/m3, 2003; Norway: TWA 0.1 ppm (0.15 mg/ m3), 1999; the Philippines: TWA 0.3 ppm (0.4 mg/m3), 1993; Poland: MAC (TWA) 0.1 mg/m3; MAC (STEL) 0.8 mg/m3, 1999; Russia: STEL 0.1 mg/m3, 1993; Sweden: NGV 0.3 ppm (0.4 mg/m3), KTV 1 ppm (1.4 mg/m3), 1999; Switzerland: MAK-W 0.1 ppm (0.15 mg/m3), KZG-W 0.2 ppm (0.3 mg/m3), 1999; Thailand: TWA 0.3 ppm (0.4 mg/m3), 1993; Turkey: TWA 0.3 ppm (0.4 mg/m3), 1993; United Kingdom: STEL 0.3 ppm (intermittent 0.42 mg/m3), 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: STEL 1 ppm. Several states have set guidelines or standards for phosphine in ambient air[60] ranging from 1.33 μg/m3 (New York) to 4.0 μg/m3 (Florida and North Dakota) to 6.7 μg/m3 (Virginia) to 8.0 μg/m3 (Connecticut) to 10.0 μg/m3 (Nevada and North Dakota) to 130 μg/m3 (North Carolina). Determination in Air: Use NIOSH Analytical Method #1003, Phosphine, OSHA Analytical Method ID-180. See also NIOSH Analytical Method #6002. Permissible Concentration in Water: No criteria set, but EPA[32] has suggested a permissible ambient goal of 5.5 μg/ L based on health effects. Determination in Water: Phosphine cannot be used to contaminate water supplies; it breaks down in water. Octanolwater coefficient: Log Kow 5 (estimated) 20.27. Routes of Entry: Phosphine can be absorbed into the body by inhalation. Direct contact with phosphine liquid may cause frostbite. Harmful Effects and Symptoms Short Term Exposure: Severe irritation to the respiratory tract. Higher exposures can cause pulmonary edema, a medical emergency that can be delayed for several hours. This can cause death. Contact with the liquid may cause frostbite. May affect the central nervous system, cardiovascular system, heart, gastrointestinal tract, liver, and kidneys. Phosphine is a super-toxic gas with a probable oral lethal dose of 5 mg/kg or 7 drops for a 150-lb person. An air concentration of 3 ppm is safe for long-term exposure,
500 ppm is lethal in 30 min, and concentration of 1000 ppm is lethal after a few breaths. Acute exposure to phosphine usually results in headache, cough, tightness and pain in the chest, shortness of breath, dizziness, lethargy, and stupor. Fatigue, muscle pain, chills, tremors, loss of coordination, seizures, and coma may be seen. Pulmonary edema and cardiac arrhythmias are common. Gastrointestinal symptoms include nausea, vomiting, abdominal pain, and diarrhea. Renal (kidney) damage, hepatic (liver) damage; and jaundice may also occur. Long Term Exposure: Chronic poisoning may cause toothache, swelling of the jaw, spontaneous fractures of bones. May cause anemia. May damage the liver and kidneys. The effects are cumulative. Can irritate the lungs; bronchitis may develop. Points of Attack: Respiratory system, liver. Medical Surveillance: NIOSH lists the following tests: Blood Gas Analysis; chest X-ray, electrocardiogram, pulmonary function tests: forced vital capacity, forced expiratory volume (1 s); sputum cytology; white blood cell count/ differential. For those with frequent or potentially high exposure (half the TLV or greater), the following are recommended before beginning work and at regular times after that: lung function tests. If symptoms develop or overexposure is suspected, the following may be useful: consider chest X-ray after acute overexposure. Liver function tests. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, if phosphides have been ingested, do not induce emesis. Phosphides will release phosphine in the stomach; therefore, watch for signs similar to those produced by phosphine inhalation. Administer a slurry of activated charcoal at 1 g/kg (usual adult dose: 6090 g; child dose: 2550 g). A soda can and a straw may be of assistance when offering charcoal to a child. Do not make an unconscious person vomit. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. Decontamination: This is very important. The rapid physical removal of a chemical agent is essential. If you do not have the equipment and training, do not enter the hot or the warm zone to rescue and/or decontaminate victims. Medical personnel should wear the proper PPE. If the victim cannot move, decontaminate without touching and without entering
Phosphine the hot or the warm zone. Metallic phosphides on clothes, skin, or hair can off-gas phosphine after contact with water or moisture, so a risk of secondary contamination may be present. Have the victim remove clothing; and seal contaminated clothes and personal belongings in a sealed double bag. For skin exposure to the metallic phosphides, scrape or brush all visible particles from the skin and hair. Use clean water from any source; if possible, use a hose (spray or fog to prevent injury to the victim) or other system to avoid touching the victim. Do not wait for soap or for the victim to remove clothing, begin washing immediately. Do not delay decontamination to obtain warm water; time is of the essence; use cold water instead. Immediately flush the eyes with water for at least 15 min. Use caution to avoid hypothermia in children and the elderly. Persons exposed only to phosphine gas do not pose substantial risks of secondary contamination. Vomitus containing phosphides can also offgas phosphine. Rinse the eyes, mucous membranes, or open wounds with sterile saline or water and then move away from the hot zone in an upwind and uphill direction. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear gas-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Up to 3 ppm: Sa (APF 5 10) (any supplied-air respirator). Up to 7.5 ppm: Sa:Cf (APF 5 25) (any supplied-air respirator operated in a continuous-flow mode). Up to 15 ppm: GmFS (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or back-mounted canister providing protection against the compound of concern]; SCBAF (APF 5 50) (any selfcontained breathing apparatus with a full face-piece) or SaF (APF 5 50) (any supplied-air respirator with a full facepiece). Up to 50 ppm: Sa: Pd,Pp (APF 5 1000) (any supplied-air respirator operated in a pressure-demand or other positive-pressure mode). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd, Pp (APF 5 10,000) (any self-contained breathing apparatus that has a full face-piece and is operated in a pressuredemand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: GmFS (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or back-mounted canister providing protection against the compound of
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concern] or SCBAE (any appropriate escape-type, self-contained breathing apparatus). Storage: Color Code—Red Stripe: Flammability Hazard: Store separately from all other flammable materials. Prior to working with this chemical you should be trained on its proper handling and storage. Before entering confined space where this chemical may be present, check to make sure that an explosive concentration is not a danger. Phosphine must be stored to avoid contact with oxidizers (such as perchlorates, peroxides; permanganates, chlorates, and nitrates), strong acids (such as hydrochloric, sulfuric, and nitric), oxygen, and halogenated hydrocarbons, since violent reactions occur. Store in tightly closed containers from physical damage. Use only nonsparking tools and equipment, especially when opening and closing containers of phosphine. Procedures for the handling, use, and storage of cylinders should be in compliance with OSHA 1910.101 and 1910.169, as with the recommendations of the Compressed Gas Association. Shipping: Phosphine requires a shipping label of “POISON GAS, FLAMMABLE GAS.” It falls in Hazard Class 2.3 and Packing Group I. It is a violation of transportation regulations to refill compressed gas cylinders without the express written permission of the owner. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Establish forced ventilation to keep levels below explosive limit. Stop the flow of gas if it can be done safely. If source of leak is a cylinder and the leak cannot be stopped in place, remove leaking cylinder to a safe place in the open air, and repair leak or allow cylinder to empty. Keep this chemical out of confined space, such as a sewer, because of the possibility of explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Initial isolation and protective action distances Distances shown are likely to be affected during the first 30 min after materials are spilled and could increase with time. If more than one tank car, cargo tank, portable tank, or large cylinder involved in the incident is leaking, the protective action distance may need to be increased. You may need to seek emergency information from CHEMTREC at (800) 424-9300 or seek professional environmental engineering assistance from the US EPA Environmental Response Team at (908) 548-8730 (24-h response line). Small spills (From a small package or a small leak from a large package) First: Isolate in all directions (feet/meters) 3000/1000 Then: Protect persons downwind (miles/kilometers) Day 0.4/0.6 Night 1.5/2.4
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Phosphoric acid, ortho-
Large spills (From a large package or from many small packages) First: Isolate in all directions (feet/meters) 2500/800 Then: Protect persons downwind (miles/kilometers) Day 2.7/4.4 Night 5.6/8.9 Fire Extinguishing: This chemical is a flammable gas. Poisonous gases and mists including oxides of phosphorus and phosphonic acid are produced in fire. Specially trained personnel may use fog lines to cool exposures and let the fire burn itself out. If material is on fire or involved in a fire, do not extinguish unless flow can be stopped; use water in flooding quantities as fog; cool all affected containers with flooding quantities of water; apply water from as far a distance as possible; solid streams of water may be ineffective; use “alcohol” foam, carbon dioxide or dry chemical. Wear full protective clothing including selfcontained breathing apparatus; rubber gloves; boots and bands around legs, arms, and waist. No skin surface should be exposed. For massive fires in cargo areas, use unmanned hose holders or monitor nozzles. Move containers from fire area. The gas is heavier than air and may travel along the ground to an ignition source. Container may explode in heat of fire. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If cylinders are exposed to excessive heat from fire or flame contact, withdraw immediately to a secure location. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant ($100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. In accordance with 40CFR165, follow recommendations for the disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by contacting your local or federal environmental control agency or by contacting your regional EPA office. Controlled discharges of Phosphine may be passed through 10% NAOH solution in a scrubbing tower. The product may be discharged to a sewer.[22]
References US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Phosphine. Washington, DC: Chemical Emergency Preparedness Program Sax, N. I. (Ed.). (1986). Dangerous Properties of Industrial Materials Report, 6, No. 2, 103107 New Jersey Department of Health and Senior Services. (April 2004). Hazardous Substance Fact Sheet: Phosphine. Trenton, NJ
Phosphoric acid, ortho-
P:0590
Molecular Formula: H3O4P Common Formula: H3PO4 Synonyms: Acide phosphorique (French); Acido fosforico Spanish); Decon 4512; Evits; Orthophosphoric acid; oPhosphoric acid; Phosphorsaeureloesungen (German); Sonac; WC-Reiniger; White phosphoric acid CAS Registry Number: 7664-38-2 RTECS® Number: TB6300000 UN/NA & ERG Number: UN1805/154 EC Number: 231-633-2 [Annex I Index No.: 015-011-00-6] Regulatory Authority and Advisory Bodies US EPA Gene-Tox Program, Negative: Cell transform.— SA7/SHE. US EPA, FIFRA 1998 Status of Pesticides: RED completed. Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. FDA—over-the-counter and proprietary drug. Clean Water Act: Section 311 Hazardous Substances/RQ 40CFR117.3 (same as CERCLA, see below); Section 313 Water Priority Chemicals (57FR41331, 9/9/92). Reportable Quantity (RQ): 5000 lb (2270 kg). EPCRA Section 313 Form R de minimis concentration reporting level: 1.0%. Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations (orthophosphoric acid): Hazard Symbol: C; Risk phrases: R34; Safety phrases: S1/2; S26; S45 (see Appendix 4). WGK (German Aquatic Hazard Class): 1—Low hazard to waters. Description: Phosphoric acid is a colorless, odorless, crystalline solid, or thick syrupy liquid. Physical state is strength and temperature dependent. Molecular weight 5 98.00; Specific gravity (H2O:1) 5 1.87 (pure); 1.33 (50% solution) at 25 C; Boiling point 5 Decomposes below BP at 212.8 C; Freezing/Melting point 5 42.2 C; Vapor pressure 5 0.03 mmHg at 20 C. Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 0, Reactivity 2 (Corrosive). Highly soluble in water.
Phosphoric acid, orthoPotential Exposure: Compound Description: Mutagen, Human Data; Primary Irritant. Phosphoric acid is used in the manufacture of fertilizers, phosphate salts; polyphosphates, detergents, activated carbon; animal feed; ceramics, dental cement; pharmaceuticals, soft drinks; gelatin, rust inhibitors; wax, and rubber latex. Exposure may also occur during electropolishing, engraving, photoengraving, lithographing, metal cleaning; sugar refining; and water-treating. Incompatibilities: The substance is a medium strong acid. Incompatible with strong caustics; most metals. Readily attacks and reacts with metals forming flammable hydrogen gas. Do not mix with solutions containing bleach or ammonia. Violently polymerizes on contact with azo compounds; epoxides, and other polymerizable compounds. Decomposes on contact with metals, alcohols, aldehydes, cyanides, ketones, phenols, esters, sulfides, halogenated organics; producing toxic fumes. Permissible Exposure Limits in Air OSHA PEL: 1 mg/m3 TWA. NIOSH REL: 1 mg/m3 TWA; 3 mg/m3 STEL. ACGIH TLV®[1]: 1 mg/m3 TWA; 3 mg/m3 STEL. NIOSH IDLH: 1000 mg/m3. Protective Action Criteria (PAC) TEEL-0: 1 mg/m3 PAC-1: 3 mg/m3 PAC-2: 500 mg/m3 PAC-3: 500 mg/m3 DFG MAK: 2 mg/m3, inhalable fraction TWA; Peak Limitation Category I(2); Pregnancy risk Group C. Arab Republic of Egypt: TWA 1 mg/m3, 1993; Australia: TWA 1 mg/m3; STEL 3 mg/m3, 1993; Austria: MAK 1 mg/ m3, 1999; Belgium: TWA 1 mg/m3; STEL 3 mg/m3, 1993; Denmark: TWA 1 mg/m3, 1999; Finland: TWA 1 mg/m3; STEL 3 mg/m3 [skin]1999; France: VME 1 mg/m3, VLE 3 mg/m3, 1999; Japan 1 mg/m3, 1999; the Netherlands: MAC-TGG 1 mg/m3, 2003; Poland: MAC (TWA) 1 mg/m3; MAC (STEL) 3 mg/m3, 1999; Sweden: NGV 1 mg/m3, KTV 3 mg/m3, 1999; Switzerland: MAK-W 1 mg/m3, 1999; Thailand: TWA 1 mg/m3, 1993; United Kingdom: STEL 2 mg/m3, 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: STEL 3 mg/m3. Several states have set guidelines or standards for phosphoric acid in ambient air[60] ranging from 1.4 μg/m3 (Massachusetts) to 1030 μg/m3 (North Dakota) to 1033 μg/m3 (Virginia) to 20.0 μg/m3 (Connecticut) to 24.0 μg/m3 (Nevada) to 25.0 μg/m3 (South Carolina). Determination in Air: Use NIOSH Analytical Method (IV) #7903, Inorganic Acids; OSHA Analytical Method ID-165SG. Determination in Water: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Corrosive to the eyes, skin, and respiratory tract. Eye contact may cause permanent damage. Inhalation can cause pulmonary edema, a medical
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emergency that can be delayed for several hours. This can cause death. Solid is especially irritating to skin in the presence of moisture. Corrosive if swallowed. May cause pain in the throat and stomach, nausea, vomiting, and intense thirst. Severe exposures may result in shock with clammy skin, weak and rapid pulse; shallow breathing; reduced urine output; and death. 15 mg/m3 may cause irritation of nose and throat. 411 mg/m3 may cause coughing. Inhalation of acid mist can cause lung irritation. 15 mg/ m3 may cause irritation of nose and throat. 411 mg/m3 may cause coughing. Long Term Exposure: Repeated or prolonged skin exposure may cause irritation, drying, cracking, and dermatitis. Can cause bronchitis to develop. Points of Attack: Eyes, skin, respiratory system. Medical Surveillance: Before beginning employment and at regular times after that, the following is recommended: lung function tests. If symptoms develop or overexposure is suspected, the following may be useful: consider chest X-ray after acute overexposure. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. If victim is conscious, administer water or milk. Do not induce vomiting. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. Natural rubber, Neoprene™, nitrile 1 pvc, nitrile, Saranex™, and polyvinyl chloride are among the recommended protective materials. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash or dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: 25 mg/m3: Sa:Cf (APF 5 25) (any supplied-air respirator operated in a continuous-flow mode). 50 mg/m3: 100F (APF 5 50) (any air-purifying, full-facepiece respirator with an N100, R100, or P100 filter) or
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Phosphorous acid
SCBAF (APF 5 50) (any self-contained breathing apparatus with a full face-piece) or SaF (APF 5 50) (any supplied-air respirator with a full face-piece). 1000 mg/m3: SaF: Pd,Pp (APF 5 2000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd, Pp (APF 5 10,000) (any self-contained breathing apparatus that has a full face-piece and is operated in a pressuredemand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: 100F (APF 5 50) (any air-purifying, full-face-piece respirator with an N100, R100, or P100 filter) or SCBAE (any appropriate escape-type, self-contained breathing apparatus). Note: Substance reported to cause eye irritation or damage; may require eye protection. Storage: Color Code—White: Corrosive or Contact Hazard; Store separately in a corrosion-resistant location. Prior to working with this chemical you should be trained on its proper handling and storage. Phosphoric acid must be stored to avoid contact with metals, aldehydes, cyanides, mercaptans, and sulfides, because violent reactions occur. Shipping: This compound requires a shipping label of “CORROSIVE.” It falls in Hazard Class 8 and Packing Group III. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: Phosphoric acid is a noncombustible solid or liquid. Contact with common metals may form flammable hydrogen gas. Use extinguishing agent suitable for surrounding fire. Use water only to keep fireexposed containers cool and to flush away spills. Poisonous gases are produced in fire, including oxides of phosphorus. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position.
If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Add slowly to solution of soda ash and slaked lime with stirring, then flush to sewer with large volumes of water. References Sax, N. I. (Ed.). (1983). Dangerous Properties of Industrial Materials Report, 3, No. 4, 8487 New York State Department of Health. (April 1986). Chemical Fact Sheet: Phosphoric Acid (Version 2). Albany, NY: Bureau of Toxic Substance Assessment US Environmental Protection Agency, Special Review and Reregistration Division Office of Pesticide Programs. (1998). Agency Status of Pesticides in Registration, Reregistration, and Special Review (Rainbow Report). Washington, DC New Jersey Department of Health and Senior Services. (April 2004). Hazardous Substances Fact Sheet: Phosphoric Acid. Trenton, NJ
Phosphorous acid
P:0600
Molecular Formula: H3O3P Common Formula: H3PO3 Synonyms: Orthophosphorus acid; Phosphonic acid; Phosphorous acid; Phosphorus trihydroxide; Trihydroxy CAS Registry Number: 13598-36-2; 10294-56-1 RTECS® Number: SZ6475500 UN/NA & ERG Number: UN2834/154 EC Number: 237-066-7 [Annex I Index No.: 015-157-00-0] Regulatory Authority and Advisory Bodies Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: Hazard Symbol (13598-36-2; 10294-56-1): C; Risk phrases: R22; R35; Safety phrases: S26; S36/3739; S45 (see Appendix 4). WGK (German Aquatic Hazard Class): 1—Low hazard to waters. Description: Phosphonic acid is a white to yellow crystalline solid. Molecular weight 5 82.00; Boiling point 5 about 200 C (decomposes); Freezing/Melting point 5 74 C. Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 0, Reactivity 1. Soluble in water. Potential Exposure: Used in chemicals manufacture; a laboratory chemical. Incompatibilities: Incompatible with aliphatic amines, alkanolamines, alkylene oxides; aromatic amines; amides, ammonia, ammonium hydroxide; bases, calcium oxide; epichlorohydrin, isocyanates. Unless it is stored in airtight containers it readily absorbs oxygen forming orthophosphoric acid. Attacks some metals.
Phosphorus Permissible Exposure Limits in Air Protective Action Criteria (PAC) TEEL-0: 0.006 mg/m3 PAC-1: 0.015 mg/m3 PAC-2: 0.125 mg/m3 PAC-3: 500 mg/m3. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Orthophosphorous acid can affect you when breathed in. Contact can cause severe eye burns leading to permanent eye damage. Inhalation can irritate the eyes, skin, and respiratory tract. Long Term Exposure: Highly irritating substances can cause lung effects; bronchitis may develop. Points of Attack: Lungs. Medical Surveillance: Before beginning employment and at regular times after that, for those with frequent or potentially high exposures, the following are recommended: lung function tests. Consider chest X-ray following acute overexposure. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. If victim is conscious, administer water or milk. Do not induce vomiting. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield when working with liquid, unless full face-piece respiratory protection is worn. Wear dust-proof goggles and face shield when working with powders or dust, unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Where there is potential for exposures to solid ortho phosphorous acid, use a NIOSH/MSHA- or European Standard EN149-approved full face-piece respirator with a high-efficiency particulate filter. Greater protection is provided by a powered air-purifying respirator. Where there is potential for high exposures of liquid ortho phosphorous acid, use a NIOSH/MSHA- or European Standard EN149approved supplied-air respirator with a full face-piece
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operated in the positive-pressure mode, or with a full facepiece, hood, or helmet in the continuous-flow mode; or use a NIOSH/MSHA- or European Standard EN149-approved selfcontained breathing apparatus with a full face-piece operated in the pressure-demand or other positive-pressure mode. Storage: Color Code—White: Corrosive or Contact Hazard; Store separately in a corrosion-resistant location. Prior to working with this chemical you should be trained on its proper handling and storage. o-phosphorous acid must be stored in airtight containers away from incompatible materials listed above. Avoid contact with metals. Shipping: This compound requires a shipping label of “CORROSIVE.” It falls in Hazard Class 8 and Packing Group III. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Absorb liquids in vermiculite, dry sand, earth, or a similar material and deposit in sealed containers. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible solid or liquid. Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Poisonous gases are produced in fire, including phosphorus oxides. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Reference New Jersey Department of Health and Senior Services. (February 2001). Hazardous Substances Fact Sheet: Phosphorous Acid, ortho. Trenton, NJ
Phosphorus
P:0610
Molecular Formula: P; P4 Synonyms: Bonide blue death rat killer; Common sense cockroach and rat preparations; Exolite 405; Exolit
2154
Phosphorus
LPKN275; Exolit VPK-N 361; Fosforo blanco (Spanish); Gelber phosphor (German); Phosphore blanc (French); Phosphorous yellow; Phosphorus-31; Phosphorus elemental, white; Rat-NIP; Red phosphorus; RP (military designation); ST CC4916140; Tetraphosphor (German); Weiss phosphor (German); White phosphorus; Yellow phosphorus CAS Registry Number: 7723-14-0 (white, red); 12185-10-3 (yellow) RTECS® Number: TH3500000 UN/NA & ERG Number: UN1381 (Phosphorus, white, dry; under water, in solution; Phosphorus, yellow, dry; yellow, under water; in solution)/136; UN2447 (Phosphorus, white, molten)/136 EC Number: 231-768-7 [Annex I Index No.: 015-001-00-1] Regulatory Authority and Advisory Bodies Department of Homeland Security Screening Threshold Quantity (pounds): Theft hazard 400 (Commercial grade). Carcinogenicity: EPA: Not Classifiable as to human carcinogenicity. Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Clean Air Act: Hazardous Air Pollutants (Title I, Part A, Section 112). Clean Water Act: Section 311 Hazardous Substances/RQ 40CFR117.3 (same as CERCLA, see below); Section 313 Water Priority Chemicals (57FR41331, 9/9/92). Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 100 lb (45.4 kg). Reportable Quantity (RQ): 1 lb (0.454 kg). EPCRA Section 313 (yellow or white) Form R de minimis concentration reporting level: 1.0%. US DOT Regulated Marine Pollutant (49CFR172.101, Appendix B), severe pollutant, white, yellow dry, molten or in solution. Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations (7723-14-0): Hazard Symbol: F,T,C,N; Risk phrases: R17; R26/28; R35; R50; Safety phrases: S1/2; S5; S26; S38; S45; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): No value assigned. Description: Phosphorus is a white to yellow, soft, waxy solid with acrid fumes in air. White/yellow phosphorus is either a yellow or colorless, volatile, crystalline solid which darkens when exposed to light and ignites in air to form white fumes and greenish light. It has a garlic-like odor. Usually shipped or stored in water. Molecular weight 5 123.88; Boiling point 5 280 C; Freezing/Melting point 5 (decomposes) 44 C; Vapor pressure 5 0.026 mmHg at 20 C; 0.181 mmHg at 44.1 C; Autoignition temperature 5 30 C. Hazard Identification (based on NFPA-704 M Rating System): (white, red powder) Health 4, Flammability 4, Reactivity 2. Insoluble in water. Red phosphorus is a brick red, reddish-brown, or violet amorphous powder, frequently contaminated with a small amount of the yellow. Molecular weight 5 30.97; Boiling
point 5 280 C (with ignition at 200 C); Freezing/Melting point 5 416 C (sublimes); Flash point 5 260 C; Autoignition temperature 5 260 C. Hazard Identification (based on NFPA-704 M Rating System): Health 1, Flammability 1, Reactivity 1. Insoluble in water. Potential Exposure: Compound Description (white): Agricultural Chemical; Reproductive Effector; Human Data. White or yellow phosphorus is handled away from air so that exposure is usually limited. Phosphorus was at one time used for the production of matches or “lucifers” but has long since been replaced due to its chronic toxicity. It is used in the manufacture of munitions including tracer bullets, pyrotechnics, explosives, smoke bombs; and other incendiary agents; (because it spontaneously catches fire in air) and as a smoke agent (because it produces clouds of irritating white smoke). Phosphorus is used artificial fertilizers; rodenticides, phosphor bronze alloys; semiconductors, Electro-luminescent coating; and chemicals, such as phosphoric and metallic phosphides. RP is used as a choking/ pulmonary agent. Incompatibilities: Phosphorus spontaneously ignites on contact with air, producing toxic phosphorus oxide fumes. Reacts with strong bases, releasing toxic phosphine gas. Phosphorus reacts violently with oxidizers, halogens, some metals, nitrites, sulfur, and many other compounds, causing a fire and explosion hazard. White/yellow reacts with air, halogens, halides, sulfur, oxidizers, alkali hydroxides (forming gas), and metals (forming reactive phosphides). Red is a combustible solid. Friction or contact with oxidizers can cause ignition. Incompatible with many other substances. Forms gas and phosphoric acid on contact with moisture. Opened packages of red phosphorus should be stored under inert gas blanket. Permissible Exposure Limits in Air OSHA PEL (yellow): 0.1 mg/m3 TWA. NIOSH REL (yellow): 0.1 mg/m3 TWA. ACGIH TLV®[1] (yellow): 0.02 ppm/0.1 mg/m3 TWA. NIOSH IDLH: 5 mg/m3. Protective Action Criteria (PAC) RP TEEL-0: 0.05 mg/m3 PAC-1: 0.15 mg/m3 PAC-2: 3 mg/m3 PAC-3: 5 mg/m3 DFG MAK (White/yellow/red): 0.05 mg/m3, inhalable fraction TWA; Peak Limitation Category II(2); Pregnancy Risk Group C; red: No numerical value established. Arab Republic of Egypt: TWA 0.1 mg/m3, 1993; Australia: TWA 0.1 mg/m3, 1993; Belgium: TWA 0.1 mg/m3, 1993; Denmark: TWA 0.1 mg/m3, 1999; Finland: STEL 0.1 mg/m3, [skin], 1999; France: VME 0.1 mg/m3, VLE 0.3 mg/m3, 1999; Hungary: TWA 0.3 mg/m3; STEL 0.06 mg/m3, 1993; the Netherlands: MAC-TGG 0.1 mg/m3, 2003; the Philippines: TWA 0.1 mg/m3, 1993; Poland: MAC (TWA) 0.3 mg/m3, 1993; Russia: STEL 0.03 mg/m3, 1993; Switzerland: MAK-W 0.1 mg/m3, KZG-W 0.2 mg/m3, 1999; Thailand: TWA 0.1 mg/m3, 1993; Turkey: TWA 0.1 mg/m3,
Phosphorus 1993; United Kingdom: LTEL 0.1 mg/m3; STEL 0.3 mg/m3, 1993; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: TWA 0.1 mg/m3. The Czech Republic[35]: TWA 0.03 mg/m3; 0.06 mg/m3 STEL. Several states have set guidelines or standards for yellow phosphorus in ambient air[60] ranging from 0.33 μg/m3 (New York) to 1.0 μg/m3 (Florida) to 1.6 μg/m3 (Virginia) to 2.0 μg/m3 (Connecticut and Nevada) to 10.030.0 μg/m3 (North Dakota). Determination in Air: Use NIOSH Analytical Method (IV) #7905. Permissible Concentration in Water: EPA[32] has suggested a permissible ambient goal of 1.4 μg/L based on health effects. Russia[35, 43] set a MAC of 0.1 μg/L in water bodies used for domestic purposes and zero in surface water used for fishery purposes. Determination in Water: Octanolwater coefficient: Log Kow 5 (estimated) 20.27. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Yellow phosphorus can be absorbed through the skin. Harmful Effects and Symptoms Short Term Exposure: Phosphorus is corrosive to the eyes, skin, and respiratory tract. Eye contact may lead to a total destruction of the eyes. Victims may experience spontaneous hemorrhaging of phosphorus-contaminated skin and mucous membranes. Sudden death, possibly due to irregular heartbeat, may occur after relatively minor (1015%) burns. Yellow: Fumes are irritating to the respiratory tract and cause severe ocular irritation. On contact with the skin it may ignite and produce severe skin burns with blistering. Very high exposure may cause severe or fatal poisoning. Red: Irritates eyes. Corrosive if ingested. Inhalation can cause pulmonary edema, a medical emergency that can be delayed for several hours. This can cause death. May affect the kidneys, liver. Exposure may result in death. Phosphorus is classified as super toxic. The probable lethal dose is less than 5 mg/kg (a taste or less than 7 drops) for a 70-kg (150 lb) person. Signs and symptoms of acute exposure to phosphorus may be severe and occur in three stages. The first stage will involve burns, pain, shock, intense thirst; nausea, vomiting, diarrhea, severe abdominal pain; and “smoking stools.” The breath and feces may have garlicky odor. The second stage will be a symptom-free period of several days in which the patient appears to be recovering. The third stage may be severe and include nausea, bloody vomitus; diarrhea (may be bloody), jaundice, liver enlargement with tenderness; renal damage; hematuria (bloody urine), and either oliguria (little urine formation) or anuria (no urine formation). Headache, convulsions, delirium, coma, cardiac arrhythmias; and cardiovascular collapse may also occur. If phosphorus contacts the eyes, then severe irritation and burns, blepharospasm (spasmodic winking), lacrimation (tearing), and photophobia (heightened sensitivity to light) may occur. Long Term Exposure: Phosphorus may affect the bones, causing bone degeneration (especially the jaw bone, known
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as “phossy” jaw), dental pain; salivation, jaw pain and swelling. This process can extend into one or both eye sockets. Repeated low exposure can cause low blood count (anemia), weight loss; and bronchitis. May cause jaundice; liver and kidney damage; cachexia. May cause nervous system damage. Points of Attack: Respiratory system, liver, kidneys, jaw, teeth, blood, eyes, skin. Medical Surveillance: NIOSH lists the following tests: Complete Blood Count, anemia; Dental X-ray/Examination; liver function tests. Also consider EKG. Special consideration should be given to the skin, eyes, jaws, teeth, respiratory tract; and liver. Preplacement medical and dental examination with X-rays of teeth is highly recommended in the case of yellow phosphorus exposure. Poor dental hygiene may increase the risk in yellow phosphorus exposures, and any required dental work should be completed before workers are assigned to areas of possible exposure. Workers experiencing any jaw injury, tooth extraction; or any abnormal dental conditions should be removed from areas of exposure and observed. X-ray examinations may show necrosis; however, in order to prevent full development of sequestra, the disease should be diagnosed in earlier stages. Liver function should be evaluated periodically. First Aid: There is no antidote for white phosphorus toxicity. If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 30 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and brush all traces of dry chemical from skin. Submerge burning phosphorus (yellow) in water or 1% copper sulfate solution if embedded in skin, or wash exposed area with large amounts of water. Seek medical attention immediately. Skin burns from yellow phosphorus should be observed for 13 days for possible delayed effects. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece
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Phosphorus
respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: 1 mg/m3: Sa (APF 5 10) (any supplied-air respirator). 2.5 mg/m3: Sa:Cf (APF 5 25) (any supplied-air respirator operated in a continuous-flow mode). 5 mg/m3: SCBAF (APF 5 50) (any self-contained breathing apparatus with a full face-piece) or SaF (APF 5 50) (any supplied-air respirator with a full face-piece). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd,Pp (APF 5 10,000) (any self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: SCBAE (any appropriate escape-type, selfcontained breathing apparatus). Note: Substance causes eye irritation or damage; eye protection needed. Storage: Color Code—Red Stripe (7723-14-0): Flammability Hazard: Do not store in the same area as other flammable materials. Color Code—Yellow Stripe (strong reducing agent): Reactivity Hazard; Store separately in an area isolated from flammables, combustibles, or other yellow-coded materials. Prior to working with this chemical you should be trained on its proper handling and storage. Phosphorus must be stored in a cool, well-ventilated area away from heat, direct sunlight; air, organic materials; oxidizers (such as perchlorates, peroxides, permanganates, chlorates, and nitrates), since violent reactions occur. Always store away from alkaline materials because of the extreme fire hazard and because poisonous gas is produced. Always store yellow phosphorus under water and protect it from physical damage. Opened packages of red phosphorus should be stored under inert gas blanket. Sources of ignition, such as smoking and open flames, are prohibited where phosphorus is used, handled, or stored in a manner that could create a potential fire or explosion hazard. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is used, handled, or stored in a manner that could create a potential fire or explosion hazard. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: Phosphorus white, molten, requires a shipping label of “SPONTANEOUSLY COMBUSTIBLE, POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 4.2 and Packing Group III. Subsidiary Hazardous Class or Division 6.1. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Keep spilled material
wet and cover with wet sand or dirt. Collect solidified material in the most convenient and safe manner and cover with water in sealed containers. Ventilate area after cleanup is complete. Keep phosphorus out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: Phosphorus (white/yellow) is a flammable solid which ignites spontaneously in moist air. Combustion in a confined space will deplete oxygen causing asphyxiation. Poisonous gases are produced in fire, including oxides of phosphorus; and phosphoric acid if water is present. Fire may restart after it has been extinguished. Small fires: dry chemical, sand, water spray; or foam. Large fires: water spray, fog, or foam. Cool containers that are exposed to flames with water from the side until well after fire is out. White/Yellow: Deluge with water, taking care not to scatter, until fire is extinguished and phosphorus has solidified, then cover with wet sand or dirt. Red: Flood with water and when fire is extinguished, cover with wet sand or dirt. Extreme caution should be used during cleanup of the more hazardous white phosphorus. White/ Yellow: Ignites at approximately 30 C in air; ignition temperature is higher when air is dry. Black: Does not catch fire spontaneously. Red: Catches fire when heated in air to approximately 260 C and burns with formation of the pentoxide. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Controlled incineration followed by alkaline scrubbing and particulate removal equipment. References Sax, N. I. (Ed.). (1983). Dangerous Properties of Industrial Materials Report, 3, No. 4, 9093 US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Phosphorus. Washington, DC: Chemical Emergency Preparedness Program
Phosphorus oxychloride New Jersey Department of Health and Senior Services. (October 2002). Hazardous Substances Fact Sheet: Phosphorus. Trenton, NJ
Phosphorus oxychloride
P:0620
Molecular Formula: Cl3OP Common Formula: POCl3 Synonyms: Fosforoxychlorid; Oxicloruro de fosforo (Spanish); Oxychlorid fosforecny; Phosphoric chloride; Phosphorus chloride oxide; Phosphorus oxytrichloride; Phosphoryl chloride; Phosphoryl trichloride CAS Registry Number: 10025-87-3 RTECS® Number: TH4897000 UN/NA & ERG Number: UN1810/137 EC Number: 233-046-7 [Annex I Index No.: 015-009-00-5] Regulatory Authority and Advisory Bodies Department of Homeland Security Screening Threshold Quantity (pounds): Release hazard 5000 ($1.00% concentration). (1% concentration); Theft hazard 220 ($80.00% concentration). Sabotage/Contamination Hazard: A placarded amount (commercial grade). Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Clean Air Act: Accidental Release Prevention/Flammable Substances, (Section 112[r], Table 3), TQ 5 5000 lb (2270 kg). Clean Water Act: Section 311 Hazardous Substances/RQ 40CFR117.3 (same as CERCLA, see below). Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 500 lb (227 kg). Reportable Quantity (RQ): 1000 lb (454 kg). US DOT 49CFR172.101, Inhalation Hazardous Chemical. Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: Hazard Symbol: T 1 , C; Risk phrases: R14; R22; R26; R35; R48/23; Safety phrases: S1/2; S7/8; S26; S36/37/39; S45 (see Appendix 4). WGK (German Aquatic Hazard Class): 1—Low hazard to waters. Description: Phosphorus oxychloride is a clear, colorless to yellow, fuming, oily liquid with a pungent and musty odor. Molecular weight 5 153.32; Specific gravity (H2O:1) 5 1.65 at 25 C; Boiling point 5 105.6 C; Freezing/Melting point 5 1.25 C; Vapor pressure 5 40 mmHg. Hazard Identification (based on NFPA-704 M Rating System): Health 4, Flammability 0, Reactivity 3 (Corrosive). Reacts with water; decomposes with heat. Potential Exposure: Phosphorus oxychloride is used in the manufacture of pesticides, pharmaceuticals, plasticizers, gasoline additives; and hydraulic fluids. Incompatibilities: A powerful oxidizer. Violently decomposes in water, forming heat and hydrochloric and
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phosphoric acids. Violent reaction with alcohols, phenols, amines, reducing agents; combustible materials; carbon disulfide; dimethylformamide, and many other materials. Rapid corrosion of metals, except nickel and lead. Permissible Exposure Limits in Air Conversion factor: 1 ppm 5 6.27 mg/m3 at 25 C & 1 atm. OSHA PEL: None. NIOSH REL: 0.1 ppm/0.6 mg/m3 TWA; 0.5 ppm/3 mg/m3 STEL. ACGIH TLV®[1]: 0.1 ppm/0.63 mg/m3 TWA. Protective Action Criteria (PAC)* TEEL-0: 0.1 ppm PAC-1: 0.479 ppm PAC-2: 0.479 ppm PAC-3: 0.85 ppm *AEGLs (Acute Emergency Guideline Levels) & ERPGs (Emergency Response Planning Guideline) are in bold face. DFG MAK: 0.2 ppm/1.3 mg/m3 TWA; Peak Limitation Category I(1); Pregnancy Risk Group C. Australia: TWA 0.1 ppm (0.6 mg/m3); STEL 0.5 ppm, 1993; Austria: MAK 0.2 ppm (1 mg/m3), 1999; Belgium: TWA 0.1 ppm (0.63 mg/m3); STEL 0.5 ppm, 1993; Denmark: TWA 0.1 ppm (0.6 mg/m3), 1999; Finland: STEL 0.5 ppm (3 mg/m3), [skin], 1999; France: VME 0.1 ppm (0.6 mg/m3), 1999; the Netherlands: MAC-TGG 0.6 mg/m3, 2003; Russia: STEL 0.05 mg/m3, [skin], 1993; Switzerland: MAK-W 0.1 ppm (0.6 mg/m3), KZG-W 0.2 ppm (1.2 mg/ m3), 1999; Turkey: TWA 0.5 ppm (3 mg/m3), 1993; United Kingdom: TWA 0.2 ppm (1.3 mg/m3); STEL 0.6 ppm, 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: TWA 0.1 ppm. Several states have set guidelines or standards for POCl2 in ambient air[60] ranging from 6.030.0 μg/m3 (North Dakota) to 12.0 μg/m3 (Connecticut) to 14.0 μg/m3 (Nevada). Determination in Air: No method available. Permissible Concentration in Water: No criteria set. (POCl2 decomposes in water). Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Corrosive to the eyes, skin, and respiratory tract. Eye contact can cause permanent damage. Inhalation of the vapors can cause pulmonary edema, a medical emergency that can be delayed for several hours. This can cause death. This material is toxic by inhalation and ingestion and is strongly irritating to skin and tissues. It causes burns of the mucous membranes of the mouth and digestive tract; and may be fatal. Symptoms include burns and extensive reddening of eyes, pains in throat; coughing, labored breathing with a shortness of breath; dizziness, headache, weakness, nausea, vomiting, chest pain; bronchitis, bronchopneumonia, kidney, and liver damage. Long Term Exposure: May cause nephritis; kidney damage. May cause liver damage.
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Phosphorus oxychloride
Points of Attack: Eyes, skin, respiratory system, central nervous system, kidneys, liver. Medical Surveillance: Lung function tests. Test for liver and kidney functions. Consider chest X-ray following acute overexposure. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. If victim is conscious, administer water or milk. Do not induce vomiting. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pneumonitis or pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in pressure-demand or other positive-pressure mode. Storage: (1) Color Code—White stripe: Contact Hazard; Store separately; not compatible with materials in solid white category. (2) Color Code—White: Corrosive or Contact Hazard; Store separately in a corrosion resistant location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, well-ventilated area away from incompatible materials listed above. Where possible, automatically pump liquid from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal
containers involving the transfer of 5 gallons or more of this chemical should be grounded and bonded. Drums must be equipped with self-closing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosionproof electrical equipment and fittings. Shipping: This compound requires a shipping label of “CORROSIVE, POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 8 and Packing Group II. Spill Handling: Keep material out of water sources and sewers; build dikes to contain flow as necessary; use water spray to knock down vapors; Do not use water on material itself; and neutralize spilled material with crushed limestone, soda ash; or lime. For a land spill, dig a pit, pond, lagoon, or holding area to contain liquid or solid material; dike surface flow using soil, sand bags; foamed polyurethane; or foamed concrete; absorb bulk liquid with fly ash or cement powder; neutralize with agricultural lime (slaked lime), crushed limestone; or sodium bicarbonate. For a water spill, neutralize with agricultural lime (slaked lime), crushed limestone; or sodium bicarbonate; use mechanical dredges or lifts to remove immobilized masses of pollutants and precipitates; adjust pH to neutral (pH 7). For air spills apply water spray or mist to knock down vapors; vapor knock down water is corrosive or toxic and should be diked for containment. Stop leak if you can do so without risk. Do not touch spilled material. Keep combustibles (wood, paper, oil, etc.) away from spilled material. Clean up only under supervision of an expert. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Initial isolation and protective action distances Distances shown are likely to be affected during the first 30 min after materials are spilled and could increase with time. If more than one tank car, cargo tank, portable tank, or large cylinder involved in the incident is leaking, the protective action distance may need to be increased. You may need to seek emergency information from CHEMTREC at (800) 424-9300 or seek professional environmental engineering assistance from the US EPA Environmental Response Team at (908) 548-8730 (24-h response line). Small spills (From a small package or a small leak from a large package) when spilled on land First: Isolate in all directions (feet/meters) 100/30 Then: Protect persons downwind (miles/kilometers)
Phosphorus pentachloride Day 0.2/0.3 Night 0.4/0.6 Large spills (From a large package or from many small packages) First: Isolate in all directions (feet/meters) 300/100 Then: Protect persons downwind (miles/kilometers) Day 0.7/1.1 Night 1.3/2.0 when spilled in water First: Isolate in all directions (feet/meters) 100/30 Then: Protect persons downwind (miles/kilometers) Day 0.1/0.2 Night 0.2/0.3 Large spills (From a large package or from many small packages) First: Isolate in all directions (feet/meters) 200/60 Then: Protect persons downwind (miles/kilometers) Day 0.5/0.8 Night 1.4/2.3 Fire Extinguishing: This chemical reacts violently with moisture producing hydrochloric and phosphoric acids. Poisonous gases, including chlorides and phosphorus oxides, are produced in fire. Do not use water unless used in flooding quantities to control a large fire by wetting down combustibles burning in vicinity of this material. Use dry chemical, carbon dioxide, or dry sand; Do not use water on material itself. Use water spray to absorb vapors and cool all affected containers with flooding quantities of water. Apply water from as far a distance as possible. Avoid breathing vapors; keep upwind. Wear self-contained breathing apparatus. Avoid bodily contact with the material. Wear boots, protective gloves, and goggles. Do not handle broken packages without protective equipment. Wash away any material which may have contacted the body with copious amounts of water or soap and water. If contact with the material is anticipated, wear full protective clothing. Keep unnecessary people away; isolate hazard area and deny entry. Vapors are heavier than air and will collect in low areas. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Pour onto sodium bicarbonate. Spray with aqueous ammonia and add crushed ice. Neutralize and pour into drain with running water. In
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accordance with 40CFR165, follow recommendations for the disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by contacting your local or federal environmental control agency or by contacting your regional EPA office. References Sax, N. I. (Ed.). (1983). Dangerous Properties of Industrial Materials Report, 3, No. 4, 8788 US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Phosphorus Oxychloride. Washington, DC: Chemical Emergency Preparedness Program New Jersey Department of Health and Senior Services. (September 2001). Hazardous Substances Fact Sheet: Phosphorus Oxychloride. Trenton, NJ
Phosphorus pentachloride
P:0630
Molecular Formula: Cl5P Common Formula: PCl5 Synonyms: Pentacloruro de fosforo (Spanish); Phosphore (pentachlorure de) (French); Phosphoric chloride; Phosphorpentachlorid (German); Phosphorus perchloride CAS Registry Number: 10026-13-8 RTECS® Number: TB6125000 UN/NA & ERG Number: UN1806/137 EC Number: 233-060-3 [Annex I Index No.: 015-008-00-X] Regulatory Authority and Advisory Bodies Department of Homeland Security Screening Threshold Quantity (pounds): Sabotage/Contamination Hazard: A placarded amount (commercial grade). Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 500 lb (227 kg). Reportable Quantity (RQ): 500 lb (227 kg). US DOT 49CFR172.101, Inhalation Hazardous Chemical. Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: Hazard Symbol: C; Risk phrases: R14; R22; R26; R34; R48/20; Safety phrases: S1/2; S7/8; S26; S36/37/39; S45 (see Appendix 4). WGK (German Aquatic Hazard Class): No value assigned. Description: Phosphorus pentachloride is a pale yellow, fuming solid with an odor like hydrochloric acid. Molecular weight 5 208.22; Specific gravity (H2O:1) 5 3.60 at 25 C; Boiling point 5 (sublimes) 160 C; Freezing/Melting point 5 (sublimes) 162 C; Vapor pressure 5 1 mmHg at 55.6 C. Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 0, Reactivity 2 . Reacts violently with water. Potential Exposure: Phosphorus pentachloride is used as a chlorinating and dehydrating agent and as a catalyst. It is used in the manufacture of agricultural chemicals;
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Phosphorus pentachloride
chlorinated compounds; gasoline additives, plasticizers, and surfactants; and in pharmaceutical manufacture. Incompatibilities: A powerful oxidizer. Reacts with water (violent), magnesium oxide, chemically active metals, such as sodium and potassium, alkalis, amines. Hydrolyzes in water (even in humid air) to form hydrochloric acid and phosphoric acid. Corrosive to many metals, forming flammable and explosive hydrogen gas. Attacks plastic and rubber. Permissible Exposure Limits in Air OSHA PEL: 1 mg/m3 TWA. NIOSH REL: 1 mg/m3 TWA. ACGIH TLV®[1]: 0.1 ppm/1 mg/m3 TWA. NIOSH IDLH: 70 mg/m3. Protective Action Criteria (PAC) TEEL-0: 1 mg/m3 PAC-1: 3 mg/m3 PAC-2: 20 mg/m3 PAC-3: 70 mg/m3 DFG MAK: 1 mg/m3, measured as the inhalable fraction TWA; Peak Limitation Category I(1); Pregnancy Risk Group C. Australia: TWA 0.1 ppm (1 mg/m3), 1993; Austria: MAK 1 mg/m3, 1999; Belgium: TWA 0.1 ppm (0.85 mg/m3), 1993; Denmark: TWA 1 mg/m3, 1999; Finland: STEL 1 mg/m3, [skin], 1999; France: VME 0.1 ppm (1 mg/m3), 1999; Japan 0.1 ppm (0.85 mg/m3), 1999; the Netherlands: MAC-TGG 1 mg/m3, 2003; Norway: TWA 0.1 mg/m3, 1999; the Philippines: TWA 1 mg/m3, 1993; Poland: MAC (TWA) 0.3 mg/m3; MAC (STEL) 0.9 mg/m3, 1999; Russia: TWA 0.1 ppm; STEL 0.2 mg/m3, [skin], 1993; Switzerland: MAKW 1 mg/m3, KZG-W 2 mg/m3, 1999; Thailand: TWA 1 mg/ m3, 1993; Turkey: TWA 1 mg/m3, 1993; United Kingdom: TWA 0.1 ppm (0.87 mg/m3), 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: TWA 0.1 ppm Several states have set guidelines or standards for PCl5 in ambient air[60] ranging from 10.0 μg/m3 (North Dakota) to 16.0 μg/m3 (Virginia) to 20.0 μg/m3 (Connecticut) to 24.0 μg/m3 (Nevada). Determination in Air: Use NIOSH II(5), Method #S-257. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: The substance is corrosive to the eyes, skin, and respiratory tract. Corrosive if swallowed. Higher exposures can cause pulmonary edema, a medical emergency that can be delayed for several hours. Can cause death by pulmonary edema or circulation shock. Fumes cause irritation of eyes and respiratory passages. Upon ingestion, immediate pain in the mouth and throat, abdominal pain; nausea, vomiting of mucoid and “coffee-ground” material, intense thirst; clammy skin, weak and rapid pulse; shallow respiration, and circulatory shock occur. Long Term Exposure: Repeated or prolonged contact with skin may cause dermatitis. May cause lung irritation; bronchitis may develop. May cause liver and kidney damage. Points of Attack: Respiratory system, lungs, eyes, skin, liver, kidneys.
Medical Surveillance: NIOSH lists the following tests: chest X-ray; pulmonary function tests: forced vital capacity, forced expiratory volume (1 s). Consider the points of attack in preplacement and periodic physical examinations. Lung function tests. Liver and kidney function tests. Consider chest X-ray following acute overexposure. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. If victim is conscious, administer water or milk. Do not induce vomiting. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Up to 10 mg/m3: Sa* (APF 5 10) (any supplied-air respirator). Up to 25 mg/m3: Sa:Cf* (APF 5 25) (any supplied-air respirator operated in a continuous-flow mode). Up to 50 mg/m3: SCBAF (APF 5 50) (any self-contained breathing apparatus with a full facepiece); or SaF (APF 5 50) (any supplied-air respirator with a full face-piece). Up to 70 mg/m3: SaF: Pd,Pp (APF 5 2000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd, Pp (APF 5 10,000) (any NIOSH/MSHA- or European Standard EN 149-approved self-contained breathing apparatus that has a full face-piece and is operated in a pressuredemand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary, self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: GmFOv100 (APF 5 50) [any air-purifying, full-face-piece
Phosphorus pentasulfide respirator (gas mask) with a chin-style, front- or backmounted organic vapor canister having an N100, R100, or P100 filter] or SCBAE (any appropriate escape-type, selfcontained breathing apparatus). *Substance reported to cause eye irritation or damage; may require eye protection. Storage: (1) Color Code—White: Corrosive or Contact Hazard; Store separately in a corrosion resistant location. (2) Color Code—Yellow Stripe (strong oxidizer): Reactivity Hazard; Store separately in an area isolated from flammables, combustibles, or other yellow-coded materials. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, well-ventilated area away from all other combustible and oxidizable materials, and moisture. Where possible, automatically transfer material storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of this chemical should be grounded and bonded. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: This compound requires a shipping label of “CORROSIVE.” It falls in Hazard Class 8 and Packing Group II. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Keep material out of water sources and sewers. Use water spray to knock down vapors. Do not use water on material itself; neutralize spilled material with crushed limestone, soda ash, or lime. Avoid breathing vapors; keep upwind. Avoid bodily contact with the materials. Do not handle broken packages without protective equipment. Wash away any materials which may have contacted the body with copious amounts of water or soap and water. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Initial isolation and protective action distances Distances shown are likely to be affected during the first 30 min after materials are spilled and could increase with time. If more than one tank car, cargo tank, portable tank, or large cylinder involved in the incident is leaking, the protective action distance may need to be increased. You may need to seek emergency information from CHEMTREC at (800) 424-9300 or seek professional environmental engineering assistance from the US EPA Environmental Response Team at (908) 548-8730 (24-h response line).
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Small spills (From a small package or a small leak from a large package) when spilled in water First: Isolate in all directions (feet/meters) 100/30 Then: Protect persons downwind (miles/kilometers) Day 0.1/0.2 Night 0.2/0.3 Large spills (From a large package or from many small packages) First: Isolate in all directions (feet/meters) 100/30 Then: Protect persons downwind (miles/kilometers) Day 0.3/0.5 Night 1.0/1.5 Fire Extinguishing: A noncombustible solid. If material is involved in fire then use dry chemical, carbon dioxide, or dry sand. Do not use water on material itself. If large quantities of combustibles are involved, use water in flooding quantities (i.e., spray or fog), and use water spray to absorb vapors. Avoid breathing vapors; keep upwind. Wear selfcontained breathing apparatus. Avoid bodily contact with the material; wear boots, protective gloves, and goggles. Poisonous gases are produced in fire, including hydrogen chloride and phosphorus oxide. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. Containers may explode in fire. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Decompose with water, forming phosphoric and hydrochloric acids. Neutralize acids and dilute if necessary for discharge into the sewer system. References US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Phosphorus Pentachloride. Washington, DC: Chemical Emergency Preparedness Program New Jersey Department of Health and Senior Services. (August 1999). Hazardous Substances Fact Sheet: Phosphorus Pentachloride. Trenton, NJ
Phosphorus pentasulfide
P:0640
Molecular Formula: P2S5; P4S10 Common Formula: P4S10 Synonyms: Pentasulfure de phosphore (French); Phosphoric sulfide; Phosphorus pentasulfide; Phosphorus persulfide;
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Phosphorus pentasulfide
Phosphorus sulfide; Sulphur phosphide; Thiophosphoric anhydride CAS Registry Number: 1314-80-3 RTECS® Number: TH4375000 UN/NA & ERG Number: UN1340 (free from yellow or white phosphorus)/139 EC Number: 215-242-4 [Annex I Index No.: 015-104-00-1] Regulatory Authority and Advisory Bodies Department of Homeland Security Screening Threshold Quantity (pounds): Sabotage/Contamination Hazard: A placarded amount (commercial grade). Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. US EPA Hazardous Waste Number (RCRA No.): U189. RCRA, 40CFR261, Appendix 8 Hazardous Constituents. Reportable Quantity (RQ): 100 lb (45.4 kg). Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: Hazard Symbol: F, Xn, N; Risk phrases: R11; R20/22; R29; Safety phrases: S2; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): 3—Severe hazard to waters. Description: Phosphorus pentasulfide is a greenish-gray to yellow, crystalline solid with an odor of rotten eggs. The odor threshold is 0.005 ppm. Molecular weight 5 222.24 (P2S5); 444.6 (P4S10); Specific gravity (H2O:1) 5 2.09; Boiling point 5 513.8 C; Freezing/Melting point 5 286 C; Vapor pressure 5 1 mmHg at 300 C; Autoignition temperature (dry air) 5 142 C. Hazard Identification (based on NFPA-704 M Rating System): Health 1, Flammability 2, Reactivity . Reacts with water. Potential Exposure: Compound Description: Primary Irritant. Phosphorus pentasulfide is used as an intermediate in the manufacture of lubricant additives, insecticides, flotation agents, lubricating oil, ignition compounds, and matches. It is also used to introduce sulfur into rubber, and organic chemicals, such as pharmaceuticals. Incompatibilities: Flammable solid; water reactive. Violent reaction with water, alcohols, strong oxidizers, acids, alkalis. Reaction with water to produce heat, hydrogen sulfide, sulfur dioxide, and phosphoric acid. May self-ignite in moist air. Permissible Exposure Limits in Air OSHA PEL: 1 mg/m3 TWA. NIOSH REL: 1 mg/m3 TWA; 3 mg/m3 STEL. ACGIH TLV®[1]: 1 mg/m3 TWA; 3 mg/m3 STEL. NIOSH IDLH: 250 mg/m3. Protective Action Criteria (PAC) TEEL-0: 1 mg/m3 PAC-1: 3 mg/m3 PAC-2: 50 mg/m3 PAC-3: 250 mg/m3 Australia: TWA 1 mg/m3; STEL 3 mg/m3, 1993; Austria: MAK 1 mg/m3, 1999; Belgium: TWA 1 mg/m3; STEL 3 mg/m3, 1993; Denmark: TWA 1 mg/m3, 1999; Finland:
STEL 1 mg/m3, 1999; France: VME 1 mg/m3, 1999; the Netherlands: MAC-TGG 1 mg/m3, 2003; the Philippines: TWA 1 mg/m3, 1993; Poland: TWA 1 mg/m3; STEL 3 mg/ m3, 1999; Switzerland: MAK-W 1 mg/m3, KZG-W 2 mg/ m3, 1999; Thailand: TWA 1 mg/m3, 1993; Turkey: TWA 1 mg/m3, 1993; United Kingdom: TWA 1 mg/m3; STEL 3 mg/m3, 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: STEL 3 mg/m3. Several states have set guidelines or standards for P2S5 in ambient air[60] ranging from 10 μg/m3 (North Dakota) to 16 μg/m3 (Virginia) to 20 μg/m3 (Connecticut) to 24 μg/m3 (Nevada). Determination in Air: No method available. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Severely irritates the eyes, skin, and respiratory tract. Inhalation of fumes produced by phosphorus compounds may cause irritation of pulmonary tissues with resultant acute pulmonary edema. The hazards of phosphorus pentasulfide are the same as for hydrogen sulfide to which it rapidly hydrolyzes in the presence of moisture. Symptoms include apnea, coma, convulsions, lacrimation (discharge of tears), photophobia (abnormal visual intolerance to light), kerato-conjunctivitis, corneal vesiculation, respiratory system irritation, dizziness, headaches, fatigue, irritability, insomnia, gastrointestinal disturbances. Long Term Exposure: Chronic exposure may lead to lung irritation, cough, bronchitis, and pneumonia. Points of Attack: Respiratory system, lungs, central nervous system, eyes, skin. Medical Surveillance: NIOSH lists the following tests: chest X-ray; pulmonary function tests: forced vital capacity, forced expiratory volume (1 s). Consider the points of attack in preplacement and periodic physical examinations. Lung function tests. Consider chest X-ray following acute overexposure. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin
Phosphorus pentoxide contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Up to 10 mg/m3 Sa (APF 5 10) (any supplied-air respirator).* Up to 25 mg/m3: Sa:Cf (APF 5 25) (any supplied-air respirator operated in a continuous-flow mode).* Up to 50 mg/m3: SCBAF (APF 5 50) (any self-contained breathing apparatus with a full facepiece) or SaF (APF 5 50) (any supplied-air respirator with a full face-piece). Up to 250 mg/m3: SaF: Pd,Pp (APF 5 2000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode). Emergency or planned entry into unknown concentrations or IDLH conditions: GmFS100 (APF 5 50) [Any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or back-mounted canister providing protection against the compound of concern and having an N100, R100, or P100 filter] or SCBAE (any appropriate escape-type, self-contained breathing apparatus). *Substance reported to cause eye irritation or damage; may require eye protection. Storage: Color Code—Red: Flammability Hazard: Store in a flammable materials storage area. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, well-ventilated area away from moisture, water, alcohols, strong oxidizers, acids, alkalis. Where possible, automatically transfer material from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of this chemical should be grounded and bonded. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: This compound requires a shipping label of “DANGEROUS WHEN WET, FLAMMABLE SOLID.” It falls in Hazard Class 4.3 and Packing Group II. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If
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employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible solid. Use dry chemical, carbon dioxide, sand. Consider the use of sodium chloride-base extinguisher suitable for metal fires. Do not use water. Poisonous gases are produced in fire, including phosphorus oxides and fluorine. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. Containers may explode in fire. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant ($100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. Decompose with water, forming phosphoric acid, sulfuric acid, and hydrogen sulfide. Provisions must be made for scrubbing hydrogen sulfide emissions. The acids may then be neutralized and diluted slowly to solution of soda ash and slaked lime with stirring, then flush to sewer with large volumes of water. Reference Sax, N. I. (Ed.). (1983). Dangerous Properties of Industrial Materials Report, 3, No. 4, 8990
Phosphorus pentoxide
P:0650
Molecular Formula: O5P2 Common Formula: P2O5 Synonyms: Diphosphorus pentoxide; Pentoxido de fosforo (Spanish); Phosphoric anhydride; Phosphorus(V) oxide; Phosphorus(51) oxide; Phosphorus pentaoxide; Phosphorus oxide; POX CAS Registry Number: 1314-56-3 RTECS®Number: TH3945000 UN/NA & ERG Number: UN1807/137 EC Number: 215-236-1 [Annex I Index No.: 015-010-00-0] Regulatory Authority and Advisory Bodies Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. US EPA, FIFRA 1998 Status of Pesticides: Active registration. Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 10 lb (4.54 kg).
2164
Phosphorus pentoxide
Reportable Quantity (RQ): 1 lb (0.454 kg). Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: Hazard Symbol: C; Risk phrases: R35; Safety phrases: S1/2; S22; S26; S45 (see Appendix 4). WGK (German Aquatic Hazard Class): 1—Low hazard to waters. Description: Phosphorus pentoxide is a white crystalline solid. Molecular weight 5 141.94; Freezing/Melting point 5 340 C; it begins to sublime at 360 C. Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 0, Reactivity 2 (Corrosive). Reacts with water. Potential Exposure: This material is used as an intermediate in organic synthesis; as a catalyst, condensing agent, dehydrating agent; in the preparation of acrylate esters, surfactants, sugar refining; in medicine, fire extinguishing, and special glasses. Incompatibilities: Reacts violently with water, forming highly corrosive phosphoric acid. Phosphorus pentoxide reacts violently with the following: perchloric acid, ammonia, hydrofluoric acid, oxidizers, hydrogen fluoride, formic acid, oxygen difluoride, potassium, sodium, propargyl alcohol, calcium oxide, inorganic bases, sodium hydroxide, and chlorine trifluoride. Attacks many metals in the presence of water. Permissible Exposure Limits in Air Protective Action Criteria (PAC)* TEEL-0: 1 mg/m3 PAC-1: 1 mg/m3 PAC-2: 10 mg/m3 PAC-3: 50 mg/m3 *AEGLs (Acute Emergency Guideline Levels) & ERPGs (Emergency Response Planning Guideline) are in bold face. DFG MAK: 2 mg/m3, measured as inhalable fraction TWA; Peak Limitation Category I(2); Pregnancy Risk Group C. Austria: MAK 1 mg/m3, 1999; Denmark: ceiling 1 mg/m3, 1999; France: VME 1 mg/m3, 1999; Hungary: TWA 1 mg/ m3; STEL 2 mg/m3, 1993; Norway: TWA 1 mg/m3, 1999; Poland: MAC (TWA) 1 mg/m3; STEL 3 mg/m3, 1999; Russia: STEL 1 mg/m3, [skin], 1993; the Netherlands: MAC-TGG 1 mg/m3, 2003; Turkey: TWA 1 mg/m3, 1993; United Kingdom: STEL 2 mg/m3, 2000. Permissible Concentration in Water: No criteria set (reacts with water). Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Highly corrosive to the eyes, skin, and respiratory tract. Eye contact may lead to a total destruction of the eyes. Particles in contact with eyes react vigorously and even a small amount may cause permanent burns. Contact with the skin will cause severe burns. Corrosive if ingested; will damage the gastrointestinal tract.
Higher exposures can cause pulmonary edema, a medical emergency that can be delayed for several hours. This can cause death. Signs and symptoms of acute exposure to phosphorus pentoxide may include severe burns, pain, shock, intense thirst, nausea, vomiting, diarrhea, severe abdominal pain; and “smoking stools.” The breath and feces may have a garlicky odor. A symptom-free period of several days may follow. Exposure to phosphorus pentoxide may also result in bloody vomitus and diarrhea, jaundice, liver enlargement with tenderness, renal damage, hematuria (bloody urine), and either oliguria (scanty urination) or anuria (suppression of urine formation). Headache, convulsions, delirium, coma, cardiac arrhythmias, and cardiovascular collapse may occur. If phosphorus pentoxide contacts the eyes, severe irritation and burns, blepharospasm (spasmodic winking), lacrimation (tearing), and photophobia (heightened sensitivity to light) may occur. Victims may experience spontaneous hemorrhaging of phosphorus pentoxide-contaminated skin and mucous membranes. Long Term Exposure: Highly corrosive materials can cause lung damage; bronchitis may develop. Points of Attack: Lungs, skin, eyes, Medical Surveillance: Lung function tests. Consider chest X-ray following acute overexposure. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. If victim is conscious, administer water or milk. Do not induce vomiting. Obtain authorization and/or further instructions from the local hospital for administration of an antidote or performance of other invasive procedures. Rush to a health-care facility. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Never pour water into this substance; always add POX slowly to water when diluting or dissolving. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a
Phosphorus trichloride NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—White: Corrosive or Contact Hazard; Store separately in a corrosion-resistant location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, well-ventilated area away from incompatible materials listed above. Shipping: This compound requires a shipping label of “CORROSIVE.” It falls in Hazard Class 8 and Packing Group II. Spill Handling: Keep unnecessary people away. Stay upwind. Keep out of low areas. Ventilate closed spaces before entering them. Stop leak if possible without risk. Do not touch spilled material. Use water spray to reduce vapors, but do not put water on leak or spill. Keep combustibles away from spilled material. Dike spilled area and keep water away from spill. Clean up requires supervision by an expert. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: Does not support combustion. For small fires, use dry chemical, carbon dioxide, or sand. Do not use water or hydrous extinguishers. Wear positive pressure breathing apparatus and special protective clothing. Keep combustibles away from spilled material. Poisonous gases, including phosphorus oxides, are produced in fire. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. For large fires, flood fire area with water from a distance. Do not get solid stream of water on spilled material or in open containers. From a secure, explosion-proof location, use water spray to cool exposed containers long after flames have been extinguished. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Decompose with water, forming phosphoric and hydrochloric acids. The acids may then
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be neutralized and diluted slowly to solution of soda ash and slaked lime with stirring then flush to sewer with large volumes of water. References US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Phosphorus Pentoxide. Washington, DC: Chemical Emergency Preparedness Program US Environmental Protection Agency, Special Review and Reregistration Division Office of Pesticide Programs. (1998). Agency Status of Pesticides in Registration, Reregistration, and Special Review (Rainbow Report). Washington, DC
Phosphorus trichloride
P:0660
Molecular Formula: Cl3P Common Formula: PCl3 Synonyms: Chloride of phosphorus; Phosphore (trichlorure de) (French); Phosphorous chloride; Phosphortrichlorid (German); Phosphorus chloride; Trichloro; Tricloruro de fosforo (Spanish) CAS Registry Number: 7719-12-2 RTECS® Number: TH3675000 UN/NA & ERG Number: UN1809/137 EC Number: 231-749-3 [Annex I Index No.: 015-007-00-4] Regulatory Authority and Advisory Bodies Department of Homeland Security Screening Threshold Quantity (pounds): Release hazard 15,000 (1% concentration); Theft hazard 45 ($3.48% concentration); Sabotage/ Contamination Hazard: A placarded amount (commercial grade). Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Clean Air Act: Accidental Release Prevention/Flammable Substances, (Section 112[r], Table 3), TQ 5 15,000 lb (6810 kg). Clean Water Act: Section 311 Hazardous Substances/RQ 40CFR117.3 (same as CERCLA, see below). Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 1000 lb (454 kg). Reportable Quantity (RQ): 1000 lb (454 kg). US DOT 49CFR172.101, Inhalation Hazardous Chemical. Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: Hazard Symbol: T 1 , C; Risk phrases: R14; R26/28; R48/20; Safety phrases: S1/ 2; S7/8; S26; S36/37/39; S45 (see Appendix 4). WGK (German Aquatic Hazard Class): 1—Low hazard to waters. Description: Phosphorus trichloride is a colorless to yellow, fuming liquid with an odor like hydrochloric acid. Molecular weight 5 137.32; Specific gravity (H2O:1) 5 1.58; Boiling point 5 76.1 C; Freezing/Melting
2166
Phosphorus trichloride
point 5 112.2 C; Vapor pressure 5 100 mmHg at 20 C. Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 0, Reactivity 2 . Reacts with water. Potential Exposure: Phosphorus trichloride is used as an intermediate and as a chlorinating agent and catalyst; in the manufacture of agricultural chemicals, pharmaceuticals, chlorinated compounds, dyes, gasoline additives, acetyl cellulose, phosphorus oxychloride, plasticizers, saccharin, and surfactants. Incompatibilities: Violent reaction with alcohols, phenols and bases, water, when in contact with combustible organics, chemically active metals: sodium, potassium, aluminum, strong nitric acid. Violent reaction with water, producing heat and hydrochloric and phosphorous acids. Attacks most metals. Attacks plastics, rubber, and coatings. Permissible Exposure Limits in Air Conversion factor: 1 ppm 5 5.62 mg/m3 at 25 C & 1 atm. OSHA PEL: 0.5 ppm/3 mg/m3 TWA. NIOSH REL: 0.2 ppm/1.5 mg/m3 TWA; 0.5 ppm/3 mg/m3 STEL. ACGIH TLV®[1]: 0.2 ppm/1.1 mg/m3 TWA; 0.5 ppm/ 2.8 mg/m3 STEL. NIOSH IDLH: 25 ppm. Protective Action Criteria (PAC)* TEEL-0: 0.34 ppm PAC-1: 0.34 ppm PAC-2: 2 ppm PAC-3: 5.6 ppm *AEGLs (Acute Emergency Guideline Levels) & ERPGs (Emergency Response Planning Guideline) are in bold face. DFG MAK: 0.5 ppm/2.8 mg/m3 TWA; Peak Limitation Category I(1); Pregnancy Risk Group C. Arab Republic of Egypt: TWA 0.5 ppm (3 mg/m3), 1993; Australia: TWA 0.2 ppm (1.5 mg/m3); STEL 0.5 ppm (3 mg/m3), 1993; Austria: MAK 0.25 ppm (1.5 mg/m3), 1999; Belgium: TWA 0.2 ppm (1.1 mg/m3); STEL 0.5 ppm (2.8 mg/m3), 1993; Denmark: TWA 0.2 ppm (1.2 mg/m3), 1999; Finland: STEL 0.5 ppm (3 mg/m3), [skin], 1999; France: VME 0.2 ppm (1.5 mg/m3), 1999; the Netherlands: MAC-TGG 1.5 mg/m3, 2003; Japan 0.2 ppm (1.1 mg/m3), 1999; Norway: TWA 0.2 ppm (1.5 mg/m3), 1999; the Philippines: TWA 0.5 ppm (3 mg/m3), 1993; Poland: MAC (TWA) 3 mg/m3, 1999; Russia: TWA 0.2 ppm; STEL 0.2 mg/m3, [skin], 1993; Turkey: TWA 0.5 ppm (3 mg/m3), 1993; United Kingdom: TWA 0.2 ppm (1.1 mg/m3); STEL 0.5 ppm, 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: STEL 0.5 ppm. Several states have set guidelines or standards for PCl3 in ambient air[60] ranging from 1530 μg/m3 (North Dakota) to 30 μg/m3 (Connecticut) to 36 μg/m3 (Nevada). Determination in Air: Use NIOSH Analytical Method 6402. Routes of Entry: Inhalation, ingestion, skin and/or eye contact.
Harmful Effects and Symptoms Short Term Exposure: Corrosive to the eyes, skin, and respiratory tract. Corrosive if swallowed. Inhalation can cause pulmonary edema, a medical emergency that can be delayed for several hours. Very high levels of exposure to vapors can cause death. This material is highly toxic; it may cause death or permanent injury. Exposure may cause dizziness, headache, anorexia, respiratory difficulties, nausea, and vomiting. It can also cause liver and lung disturbances. Occupational exposure has caused coughs, bronchitis, pneumonia, and conjunctivitis. Long Term Exposure: Highly corrosive materials can cause lung damage; bronchitis may develop. Points of Attack: Eyes, skin, respiratory system. Medical Surveillance: NIOSH lists the following tests: chest X-ray, electrocardiogram, pulmonary function tests: forced vital capacity, forced expiratory volume (1 s); sputum cytology; white blood cell count/differential. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 30 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. If victim is conscious, administer water or milk. Do not induce vomiting. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: 10 ppm: SCBAF (APF 5 50) (any self-contained breathing apparatus with a full face-piece) or SaF (APF 5 50) (any supplied-air respirator with a full face-piece). 25 ppm: SaF: Pd,Pp (APF 5 2000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd,Pp (APF 5 10,000) (any
Phosphorus trichloride self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positivepressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: GmFS (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or back-mounted canister providing protection against the compound of concern] or SCBAE (any appropriate escape-type, self-contained breathing apparatus). Note: Substance causes eye irritation or damage; eye protection needed. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Phosphorus trichloride must be stored to avoid contact with acetic acid, aluminum, chromyl chloride, fluorine, alcohol, nitric acid, sodium, potassium, water, hydroxylamine, and lead dioxide since violent reactions occur. Store in tightly closed containers in a cool, well-ventilated area away from water and moisture. Phosphorus trichloride corrodes most metals and will attack some forms of plastics, rubber, and coatings. Shipping: This compound requires a shipping label of “POISONOUS/TOXIC MATERIALS, CORROSIVE.” It falls in Hazard Class 6.1 and Packing Group I. A plus sign (1) indicates that the designated proper shipping name and hazard class of the material must always be shown whether or not the material or its mixtures or solutions meet the definitions of the class. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Ventilate area of spill or leak. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Initial isolation and protective action distances Distances shown are likely to be affected during the first 30 min after materials are spilled and could increase with time. If more than one tank car, cargo tank, portable tank, or large cylinder involved in the incident is leaking, the protective action distance may need to be increased. You may need to seek emergency information from CHEMTREC at (800) 424-9300 or seek professional environmental
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engineering assistance from the US EPA Environmental Response Team at (908) 548-8730 (24-h response line). Small spills (From a small package or a small leak from a large package) when spilled on land First: Isolate in all directions (feet/meters) 100/30 Then: Protect persons downwind (miles/kilometers) Day 0.2/0.3 Night 0.4/0.6 Large spills (From a large package or from many small packages) First: Isolate in all directions (feet/meters) 500/150 Then: Protect persons downwind (miles/kilometers) Day 0.9/1.5 Night 1.9/3.1 when spilled in water First: Isolate in all directions (feet/meters) 100/30 Then: Protect persons downwind (miles/kilometers) Day 0.1/0.2 Night 0.2/0.3 Large spills (From a large package or from many small packages) First: Isolate in all directions (feet/meters) 200/60 Then: Protect persons downwind (miles/kilometers) Day 0.5/0.8 Night 1.7/2.7 Fire Extinguishing: This material may burn but does not easily ignite. Use carbon dioxide or dry chemical on fires involving phosphorus trichloride. Do not use water. Poisonous gases are produced in fire, including hydrogen chloride and phosphoric acid. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. Spray cooling water on containers that are exposed to flames until well after fire is out. Do not get water inside containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Decompose with water, forming phosphoric and hydrochloric acids. The acids may then be neutralized and diluted slowly to solution of soda ash and slaked lime with stirring, then flush to sewer with large volumes of water. References Sax, N. I. (Ed.). (1983). Dangerous Properties of Industrial Materials Report, 3, No. 4, 9394 US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Phosphorus
2168
Phthalic anhydride
Trichloride. Washington, DC: Chemical Emergency Preparedness Program New Jersey Department of Health and Senior Services. (March 2001). Hazardous Substances Fact Sheet: Phosphorous Trichloride. Trenton, NJ
Phthalic anhydride
P:0670
Molecular Formula: C8H4O3 Synonyms: Anhidrido ftalico (Spanish); Anhydride phthalique (French); Araldite HT 901; 1,2-Benzenedicarboxylic anhydride; 1,2-Benzenedicarboxylic acid anhydride; 1,2Dioxophthalan phthalandione; 1,3-Dioxophthalan; Esen; HT 901; 1,3-Isobenzofurandione; NCI-C03601; PAN; Phthalandione; 1,3-Phthalandione; Phthalanhydride; Phthalic acid anhydride; Phthalsaeureanhydrid (German); Retarder AK; Retarder esen; Retarder PD; TGL 6525; Vulkalent B/C CAS Registry Number: 85-44-9 RTECS® Number: TI3150000 UN/NA & ERG Number: UN2214/156 EC Number: 201-607-5 [Annex I Index No.: 607-009-00-4] Regulatory Authority and Advisory Bodies Carcinogenicity: NCI: Carcinogenesis Bioassay (feed); no evidence: mouse, rat. US EPA Gene-Tox Program, Negative: Carcinogenicity— mouse/rat. Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Clean Air Act: Hazardous Air Pollutants (Title I, Part A, Section 112). US EPA Hazardous Waste Number (RCRA No.): U190. RCRA, 40CFR261, Appendix 8 Hazardous Constituents. RCRA 40CFR268.48; 61FR15654, Universal Treatment Standards: Wastewater (mg/L), 0.055; Nonwastewater (mg/ kg), 28. Reportable Quantity (RQ): 5000 lb (2270 kg). EPCRA Section 313 Form R de minimis concentration reporting level: 1.0%. Canada, WHMIS, Ingredients Disclosure List Concentration 0.1%. European/International Regulations: Hazard Symbol: Xi; Risk phrases: R22; R37/38; R41; R42/43; Safety phrases: S2; S23; S24/25; S26; S37/39; S46 (see Appendix 4). WGK (German Aquatic Hazard Class): 1—Low hazard to waters. Description: Phthalic Anhydride is moderately flammable, white solid (flake) or a clear, colorless, mobile liquid (molten) with a characteristic, acrid, choking odor. The odor threshold is 0.05 ppm. Molecular weight 5 148.12 (flake); 1.20 (molten); Boiling point 5 (sublimes) 295 C; Freezing/ Melting point 5 130.6 C; Vapor pressure 5 0.0015 mmHg at 20 C; Flash point 5 151.7 C (cc); Autoignition temperature 5 570 C. Explosive limits: LEL 5 1.7%;
UEL 5 10.5%. Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 1, Reactivity 0. Slightly soluble in water; slow reaction. Potential Exposure: Compound Description: Tumorigen, Mutagen; Reproductive Effector; Primary Irritant. Phthalic anhydride is used in plasticizers, in the manufacture of phthaleins, benzoic acid, alkyd and polyester resins, synthetic indigo, and phthalic acid; which is used as a plasticizer for vinyl resins. To a lesser extent, it is used in the production of alizarin, dye, anthranilic acid, anthraquinone, diethyl phthalate, dimethyl phthalate, erythrosine, isophthalic acid, methylaniline, phenolphthalein, phthalamide, sulfathalidine, and terephthalic acid. It has also found uses as a pesticide intermediate. Incompatibilities: Dust forms an explosive mixture with air. Strong acids, caustics, ammonia, amines, strong oxidizers, water. Converted to phthalic acid in hot water. Reacts violently with copper oxide or sodium nitrite 1 heat. Permissible Exposure Limits in Air Conversion factor: 1 ppm 5 6.06 mg/m3 at 25 C & 1 atm. OSHA PEL: 2 ppm/12 mg/m3 TWA. NIOSH REL: 1 ppm/6 mg/m3 TWA. ACGIH TLV®[1]: 1 ppm/6.1 mg/m3 TWA; danger of sensitization; not classifiable as a human carcinogen. NIOSH IDLH: 60 mg/m3. Protective Action Criteria (PAC) TEEL-0: 12 mg/m3 PAC-1: 12 mg/m3 PAC-2: 12 mg/m3 PAC-3: 60 mg/m3 DFG MAK: Danger of skin sensitization; No numerical value established. Data may be available. Australia: TWA 1 ppm (6 mg/m3), 1993; Austria: MAK 1 mg/m3, 1999; Belgium: TWA 1 ppm (6.1 mg/m3), 1993; Denmark: TWA 2 mg/m3, 1999; Finland: TWA 0.2 mg/m3, 1999; France: VLE 6 mg/m3, 1999; Hungary: TWA 1 mg/m3; STEL 2 mg/m3, 1993; the Netherlands: MAC-TGG 1 mg/m3, 2003; Norway: TWA 2 mg/m3, 1999; the Philippines: TWA 2 ppm (12 mg/m3), 1993; Poland: MAC (TWA) 1 mg/m3; STEL 2 mg/m3 (vapors and aerosols), 1999; Russia: STEL 1 mg/m3, [skin], 1993; Sweden: NGV 2 mg/m3, TGV 3 mg/m3, 1999; Switzerland: MAK-W 1 mg/m3, KZG-W 2 mg/m3, 1999; United Kingdom: TWA 4 mg/m3; STEL 12 mg/m3, 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: not classifiable as a human carcinogen. Russia[43] set a MAC of 0.1 mg/m3 for ambient air in residential areas (100 μg/m3). Several states have set guidelines or standards for phthalic anhydride in ambient air[60] ranging from 0.82 μg/m3 (Massachusetts) to 60240 μg/m3 (North Dakota) to 100 μg/m3 (Virginia) to 120 μg/m3 (Connecticut) to 143 μg/m3 (Nevada). Determination in Air: Use NIOSH II(3), Method #S179; OSHA Analytical Method 90. Determination in Water: Octanolwater coefficient: Log Kow 5 1.58.
Phthalic anhydride Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Irritates the eyes, skin, and respiratory tract. Inhalation: May cause irritation of nose, throat, and mouth with coughing, sneezing, shortness of breath, and excessive discharge and bleeding from nose. Studies suggest that this will occur at about 4 ppm. Skin: Rapid chemical burns may occur on contact with wet skin. Molten material may cause severe burns unless removed immediately. Eyes: May cause severe irritation and chemical burns on contact or at dust levels above 5 ppm. Ingestion: May cause severe irritation to mouth and throat. Animal studies suggest that death may occur from ingestion of 48 oz. Long Term Exposure: May cause irritation of nose, mouth, throat, and lungs. Repeated or prolonged contact may cause conjunctivitis, nasal ulcer bleeding. Allergy may develop in sensitive individuals which can lead to bronchial asthma. Repeated or prolonged skin contact may cause dermatitis, skin sensitization, and allergy. In animals: liver, kidney damage. Points of Attack: Eyes, skin, respiratory system, liver, kidneys. Medical Surveillance: NIOSH lists the following tests: chest X-ray; pulmonary function tests: forced vital capacity, forced expiratory volume (1 s); urine (chemical/metabolite). Lung function tests may be normal if person is not having an attack at the time. If symptoms develop or overexposure is suspected, the following may be useful: evaluation by a qualified allergist, including careful exposure history and special testing, may help diagnose skin allergy. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. If victim is conscious, administer water or milk. Do not induce vomiting. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield when working with liquid, or wear dust-proof goggles when working with powders or dust unless full face-piece respiratory protection is worn.
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Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: NIOSH: 30 mg/m3: Qm (APF 5 25) (any quarter-mask respirator). 60 mg/m3: 95 XQ [any particulate respirator equipped with an N95, R95, or P95 filter (including N95, R95, and P95 filtering face-pieces) except quarter-mask respirators. The following filters may also be used: N99, R99, P99, N100, R100, P100] or 95F (APF 5 10) (any air-purifying full-face-piece respirator equipped with an N95, R95, or P95 filter. The following filters may also be used: N99, R99, P99, N100, R100, P100) or PaprHie (APF 5 25)* (any powered air-purifying respirator with a high-efficiency particulate filter) or SA* (any supplied-air respirator) or SCBAF (APF 5 50) (any selfcontained breathing apparatus with a full face-piece). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd,Pp (APF 5 10,000) (any self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positivepressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: 100F (APF 5 50) (any air-purifying, full-face-piece respirator with an N100, R100, or P100 filter) or SCBAE (any appropriate escape-type, self-contained breathing apparatus). *Substance reported to cause eye irritation or damage; may require eye protection. Storage: Color Code—White Stripe (flake): Contact Hazard; not compatible with materials in solid white category. Color Code—White: Corrosive or Contact Hazard; Store separately in a corrosion-resistant location. Prior to working with this chemical you should be trained on its proper handling and storage. Before entering confined space where this chemical may be present, check to make sure that an explosive concentration is not a danger. Phthalic anhydride must be stored to avoid contact with strong oxidizers (such as chlorine and bromine) since violent reactions occur. Sources of ignition (such as smoking and open flames) are prohibited where phthalic anhydride is used, handled, or stored in a manner that could create a potential fire or explosion hazard. Shipping: This compound requires a shipping label of “CORROSIVE.” It falls in Hazard Class 8 and Packing Group III. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Establish forced ventilation to keep levels below explosive limit. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated
2170
m-Phthalodinitrile
runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible solid. Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Poisonous gases are produced in fire. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Dissolve or mix the material with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber. All federal, state, and local environmental regulations must be observed. Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant ($100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. References US Environmental Protection Agency. (April 30, 1980). Phthalic Anhydride, Health and Environmental Effects Profile No. 147. Washington, DC: Office of Solid Waste New York State Department of Health. (March 1986). Chemical Fact Sheet: Phthalic Anhydride. Version 2. Albany, NY: Bureau of Toxic Substance Assessment New Jersey Department of Health and Senior Services. (August 2001). Hazardous Substances Fact Sheet: Phthalic Anhydride. Trenton, NJ
m-Phthalodinitrile
P:0680
Molecular Formula: C8H4N2 Common Formula: C6H4(CN)2 Synonyms: 1,3-Benzenedicarbonitrile; mBenzenedicarbonitrile; m-Dicyanobenzene; 1,3Dicyanobenzene; Isophthalodinitrile; m-PDN; Phthalonitrile, m-Dicyanobenzene CAS Registry Number: 626-17-5 RTECS® Number: CZ1900000 UN/NA & ERG Number: UN3276 (Nitriles, toxic, liquid, n.o.s.)/151
EC Number: 210-933-7 Regulatory Authority and Advisory Bodies Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: not listed in Annex 1. WGK (German Aquatic Hazard Class): 1—Low hazard to waters. Description: m-Phthalodinitrile is a needle-like, colorless to white, flaky solid with an almond-like odor. Molecular weight 5 128.14; Specific gravity (H2O:1) 5 4.42; Boiling point 5 sublimes; Freezing/Melting point 5 162 C (sublimes); Vapor pressure 5 0.01 mmHg at 20 C. Hazard Identification (based on NFPA-704 M Rating System): Health 2, Flammability 0, Reactivity 0. Slightly soluble in water. Potential Exposure: Compound Description: Drug, Primary Irritant. This material is used as an intermediate in the manufacture of polyurethane paints and varnishes; in pharmaceuticals, for synthetic fibers, agricultural chemicals, rubber chemicals; an intermediate for phthalocyanine pigments and dyes, and for high-temperature lubricants and coatings; it may be used to produce phthalate esters. Incompatibilities: Combustible solid. The dust is a severe explosion hazard. Strong oxidizers (e.g., chlorine, bromine, fluorine). Permissible Exposure Limits in Air OSHA PEL: None. NIOSH REL: 5 mg/m3 TWA. ACGIH TLV®[1]: 5 mg/m3, measured as inhalable fraction and vapor, TWA. No TEEL available. Australia: TWA 5 mg/m3, 1993; Belgium: TWA 5 mg/m3, 1993; Denmark: TWA 5 mg/m3, 1999; Finland: TWA 5 mg/m3; STEL 20 mg/m3, [skin], 1999; France: VME 5 mg/m3, 1999; Norway: TWA 5 mg/m3, 1999; Switzerland: MAK-W 5 mg/m3, 1999; the Netherlands: MAC-TGG 5 mg/m3, 2003; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: TWA 5 mg/m3. Several states have set guidelines or standards for m-phthalodinitrile in ambient air[60] ranging from 50 μg/m3 (North Dakota) to 100 μg/m3 (Connecticut) to 119 μg/m3 (Nevada). Determination in Air: No method available. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Absorbed by the skin. Harmful Effects and Symptoms Short Term Exposure: m-Phthalodinitrile can affect you when breathed in and by passing through your skin. High exposure may cause headache, nausea, weakness, confusion and may cause you to pass out. In animals: irritation of the eyes, skin. Long Term Exposure: May cause headaches and nausea. No permanent effects are known at this time. Points of Attack: Eyes, skin, central nervous system.
m-Phthalodinitrile First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. See NIOSH Criteria Document 212 Nitriles. Respirator Selection: Where there is potential for exposures over 5 mg/m3, use a NIOSH/MSHA- or European Standard EN149-approved full-face-piece respirator with a high-efficiency particulate filter. Greater protection is provided by a powered air-purifying respirator. Where there is potential for high exposures, use a NIOSH/MSHA- or European Standard EN149-approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuous-flow mode; or use a MSHA/NIIOSH approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. m-Phthalodinitrile is incompatible with strong oxidizers, such as chlorine, bromine, and fluorine. Store in tightly closed containers in a cool, well-ventilated area away from open flames and high temperatures. Sources of ignition, such as smoking and open flames, are prohibited where m-phthalodinitrile is used, handled, or stored in a manner that could create potential fire of explosion hazard. m-Phthalodinitrile dust is a severe explosion hazard. Use explosion proof equipment when handling mphthalodinitrile. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered
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material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Initial isolation and protective action distances: Distances shown are likely to be affected during the first 30 min after materials are spilled and could increase with time. If more than one tank car, cargo tank, portable tank, or large cylinder involved in the incident is leaking, the protective action distance may need to be increased. You may need to seek emergency information from CHEMTREC at (800) 4249300 or seek professional environmental engineering assistance from the US EPA Environmental Response Team at (908) 548-8730 (24-h response line). Small spills (From a small package or a small leak from a large package) First: Isolate in all directions (feet/meters) 100/30 Then: Protect persons downwind (miles/kilometers) Day 0.1/0.1 Night 0.1/0.2 Large spills (From a large package or from many small packages) First: Isolate in all directions (feet/meters) 200/60 Then: Protect persons downwind (miles/kilometers) Day 0.3/0.5 Night 0.5/0.9 Fire Extinguishing: This chemical is a combustible solid. Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Poisonous gases are produced in fire, including ammonia, hydrogen cyanide, and nitrogen oxides. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: React with alcoholic NaOH; after 1 h, evaporate alcohol and add calcium hypochlorite; after 24 h flush into sewer with large volumes of water. Reference New Jersey Department of Health and Senior Services. (November 2000). Hazardous Substances Fact Sheet: m-Phthalodinitrile. Trenton, NJ
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Phylloquinone
Phylloquinone
P:0690
Molecular Formula: C31H46O2 Synonyms: Antihemorrhagic vitamin; Aqua mephyton; Combinal K1; Kativ N; Kephton; Kinadion; Konakion; Mephyton; 2-Methyl-3-phythyl-1,4-naphthochinon (German); 2-Methyl-3-(3,7,11,15-tetramethyl-2-hexadecenyl)-1,4-naphthalenedione; Monodion; Phyllochinon (German); α-Phylloquinone; trans-Phylloquinone; Phytomenadione; Phytonadione; Vitamin K1 CAS Registry Number: 84-80-0 RTECS® Number: QJ5800000 EC Number: 201-564-2 Regulatory Authority and Advisory Bodies Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: Dropped From Listing in 1988). European/International Regulations: not listed in Annex 1. WGK (German Aquatic Hazard Class): No value assigned. Description: Phylloquinone is an odorless yellow viscous oil or crystals. Molecular weight 5 450.77; Boiling point 5 140145 C at 0.001 mm; Freezing/Melting point 5 4 C; 20 C. Hazard Identification (based on NFPA-704 M Rating System): Health 1, Flammability 0, Reactivity 0. Insoluble in water. Potential Exposure: Phylloquinone is a dietary component essential for normal biosynthesis of several factors required for clotting of blood, as a therapeutic drug used to correct bleeding tendency, and as a food supplement. Incompatibilities: Phylloquinone decomposes in sunlight and is destroyed by alkali hydroxides and reducing agents. Permissible Exposure Limits in Air No standards or TEEL available. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: High oral toxicity. Intravenous injection can cause toxic responses and occasionally death. Rapid intravenous administration of phylloquinone has produced flushing, irregular breathing, and chest pains. In newborns, it can cause hemolytic anemia and hemoglobinuria. In patients who have severe liver disease, administration of large doses of menadione or phylloquinone may further depress function of liver. Individuals resistant to coumarin may have unusual sensitivity to the antidotal effects of vitamin K. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical
facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Keep victim quiet and maintain normal body temperature. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—Green: General storage may be used. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, well-ventilated area away from alkali hydroxides and reducing agents. Where possible, automatically pump liquid from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of 5 gallons or more of this chemical should be grounded and bonded. Drums must be equipped with self-closing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Spill Handling: Keep unnecessary people away; isolate hazard area and deny entry. Stay upwind; keep out of low areas. Wear self-contained (positive pressure if available) breathing apparatus and full protective clothing. Shut off ignition sources; no flares, smoking, or flames in hazard area. Keep combustibles (wood, paper, oil, etc.) away from spilled material. Do not touch spilled material. Small spills: absorb with sand or other noncombustible absorbent material and place into containers for later disposal. Large spills: dike far ahead of spill for later disposal. Ventilate area of spill or leak. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless
Physostigmine the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: Irritating fumes are produced in fire. Use dry chemical, carbon dioxide, or alcohol foam extinguishers. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Reference US Environmental Protection Agency. (October 31, 1985). Chemical Hazard Information Profile: Phylloquinone. Washington, DC: Chemical Emergency Preparedness Program
Physostigmine
P:0700
Molecular Formula: C15H21N3O2 Synonyms: Calabarine; Erserine; Eserine; Eserolein; Fisostigmina (Spanish); Methylcarbamate (ester); Methylcarbamic acid, ester with eseroline; Physostol CAS Registry Number: 57-47-6 RTECS® Number: TJ2100000 UN/NA & ERG Number: UN2757(carbamate pesticides, solid, toxic)/151 see “Potential Exposure” EC Number: 200-332-8 [Annex I Index No.: 614-020-00-8] Regulatory Authority and Advisory Bodies US EPA Hazardous Waste Number (RCRA No.): P204. RCRA, 40CFR261, Appendix 8 Hazardous Constituents. RCRA 40CFR268.48; 61FR15654, Universal Treatment Standards: Wastewater (mg/L), 0.056; Nonwastewater (mg/ kg), 1.4. Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 100/10,000 lb (45.4/4540 kg). Reportable Quantity (RQ): 100 lb (45.4 kg). European/International Regulations: Hazard Symbol: T1, N; Risk phrases: R26/28; R1/2; Safety phrases: S25; S45 (see Appendix 4).
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WGK (German Aquatic Hazard Class): 3—Severe hazard to waters. Description: Physostigmine is an odorless white crystalline solid. Molecular weight 5 275.39; Freezing/Melting point 5 8687 C (unstable form); 105106 C (stable form). Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 1, Reactivity 1. Slightly soluble in water. Potential Exposure: Material is used as a cholinergic (anticholinesterase) agent and as a veterinary medication. Listed as a carbamate pesticide; however, physostigmine is not registered in the United States as such. Incompatibilities: Light and heat. Permissible Exposure Limits in Air Protective Action Criteria (PAC) TEEL-0: 0.75 mg/m3 PAC-1: 2.5 mg/m3 PAC-2: 4.5 mg/m3 PAC-3: 4.5 mg/m3 Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Super toxic. Probable oral lethal dose is less than 5 mg/kg for a 70-kg (150 lb) person. Material is a cholinesterase inhibitor. Effects of exposure may involve the respiratory, gastrointestinal, cardiovascular, and central nervous systems. Death occurs due to respiratory paralysis or impaired cardiac function. Time to death may vary from 5 min to 24 h, in severely poisoned patients, depending on factors, such as the dose and route. General symptoms include: increased secretions, fatigability and generalized weakness; involuntary twitching; severe weakness of skeletal muscles. Symptoms of exposure to material by major organ system: gastrointestinal: lack of appetite, nausea and vomiting, abdominal cramps, and diarrhea. Central nervous system: confusion, uncoordination, slurred speech, loss of reflexes, rapid irregular breathing, generalized convulsions, and coma. Cardiovascular: slowed heartbeat resulting in hypotension and fall in cardiac output. Long Term Exposure: Cholinesterase inhibitor; cumulative effect is possible. This chemical may damage the nervous system with repeated exposure, resulting in convulsions, respiratory failure. May cause liver damage. Points of Attack: Respiratory system, lungs, central nervous system, cardiovascular system, skin, eyes, plasma and red blood cell cholinesterase. Medical Surveillance: Before employment and at regular times after that, the following are recommended: plasma and red blood cell cholinesterase levels (tests for the enzyme poisoned by this chemical). If exposure stops, plasma levels return to normal in 12 weeks while red blood cell levels may be reduced for 13 months. When cholinesterase enzyme levels are reduced by 25% or more below preemployment levels, risk of poisoning is increased, even if results are in lower ranges of “normal.” Reassignment to work not involving carbamate pesticides is
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Picloram
recommended until enzyme levels recover. If symptoms develop or overexposure occurs, repeat the above tests as soon as possible and get an examination of the nervous system. Also, consider complete blood count. Consider chest X-ray following acute overexposure. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, wellventilated area. Shipping: Carbamate pesticides, solid, toxic, require a shipping label of “POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 6.1 and Packing Group I. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. As for other carbamate pesticides, avoid breathing dusts and fumes from burning materials. Keep upwind. Avoid bodily contact with the material. Wash away any material which may have contacted the body with copious amounts of water or soap and water. Remove all ignition sources. Collect powdered material in the most convenient
and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: As for other carbamate pesticides, extinguish fire using agent suitable for type of surrounding fire (material itself burns with difficulty). Use water in flooding quantities as fog. Use alcohol foam, carbon dioxide, or dry chemical. Wear self-contained breathing apparatus when fighting fires. Poisonous gases are produced in fire, including nitrogen oxides. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: In accordance with 40CFR165, follow recommendations for the disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by contacting your local or federal environmental control agency or by contacting your regional EPA office. Reference US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Physostigmine. Washington, DC: Chemical Emergency Preparedness Program
Picloram
P:0710
Molecular Formula: C6H3Cl3N2O2 Synonyms: Amdon; Amdon grazon; 4-Aminotrichloropicolinic acid; 4-Amino-3,5,6-trichloro-2-picolinic acid; 4-Amino-3,5,6-trichloropicolinic acid; 4-Amino-3,5,6-trichloro-2-pyridinecarboxylic acid; 4-Amino-3,5,6-trichloropyridine-2-carboxylic acid; 4-Amino-3,5,6-trichlorpicolinsaeure (German); ATCP; Borolin; K-Pin; NCI-C00237; NSC 233899; Picolinic acid, 4-Amino-3,5,6-trichloro-; 2Pyridine carboxylic acid, 4-amino-3,5,6-trichloro-; Tordon; Tordon 10K; Tordon 22K; Tordon 101 mixture; 3,5,6Trichloro-4-aminopicolinic acid CAS Registry Number: 1918-02-1
Picloram RTECS® Number: TJ7525000 UN/NA & ERG Number: UN2588/151 EC Number: 217-636-1 Regulatory Authority and Advisory Bodies Carcinogenicity: NCI: Carcinogenesis Bioassay (feed); equivocal evidence: rat; no evidence: mouse; IARC: Animal Limited Evidence; Human No Available Data, not classifiable as carcinogenic to humans, Group 3, 1991. US EPA, FIFRA 1998 Status of Pesticides: RED completed. Banned or Severely Restricted (Sweden) (UN).[13] Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Safe Drinking Water Act: MCL, 0.5 mg/L; MCLG, 0.5 mg/ L; Regulated chemical (47 FR 9352) as pichloram. EPCRA Section 313 Form R de minimis concentration reporting level: 1.0%. WGK (German Aquatic Hazard Class): No value assigned. Description: Picloram is a colorless powder with a chlorine-like odor. Molecular weight 5 241.46; Freezing/ Vapor Melting point 5 (decomposes) 219.8 C; 27 pressure 5 6 3 10 mmHg at 36.7 C. Poor solubility in water. Potential Exposure: Compound Description: Agricultural Chemical; Tumorigen, Mutagen; Reproductive Effector. Those involved in the manufacture, formulation, or application of the herbicide. Incompatibilities: This material is acidic. Reacts with hot concentrated alkali (hydrolyzes), strong bases. Attacks some metals. Permissible Exposure Limits in Air OSHA PEL: 15 mg/m3 TWA, total dust; 5 mg/m3 TWA, respirable fraction. NIOSH REL: See Appendix D of the NIOSH Pocket Guide. ACGIH TLV®[1]: 10 mg/m3 TWA; not classifiable as a human carcinogen. No TEEL available. Australia: TWA 10 mg/m3; STEL 20 mg/m3, 1993; Belgium: TWA 10 mg/m3; STEL 20 mg/m3, 1993; Denmark: TWA 10 mg/m3, 1999; Finland: TWA 10 mg/m3; STEL 20 mg/m3, 1999; France: VME 10 mg/m3, 1999; Russia: STEL 2 mg/m3, 1993; Switzerland: MAK-W 10 mg/m3, 1999; United Kingdom: TWA 10 mg/m3; STEL 20 mg/m3, 2000; the Netherlands: MAC-TGG 10 mg/m3, 2003; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: not classifiable as a human carcinogen. Russia set a MAC of 0.03 mg/m3 for ambient air on a oncedaily basis and 0.02 mg/m3 on a daily average basis. Several states have set guidelines or standards for picloram in ambient air[60] ranging from 0.10.2 mg/m3 (North Dakota) to 0.16 mg/m3 (Virginia) to 0.2 mg/m3 (Connecticut) to 0.238 mg/m3 (Nevada). Determination in Air: Filter; none; Gravimetric; NIOSH IV, Particulates NOR: Method #0500, total dust; Method #0600 (respirable dust).
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Permissible Concentration in Water: The US EPA has set a lifetime health advisory of 0.49 mg/L. Russia set a MAC of 10.0 mg/L in surface water. States which have set guidelines for Picloram in drinking water[61] include Kansas at 0.175 mg/L and Maine at 0.3 mg/L. Determination in Water: Fish Tox 5 703.55815000 ppb (VERY LOW). Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Irritates the eyes, skin, and respiratory tract. Exposure can cause nausea. Long Term Exposure: Picloram should be handled as a carcinogen—with extreme caution. It may damage the testes. May affect the kidneys and liver. In animals: liver, kidney changes. Human Tox 5 500.00000 ppb (VERY LOW). Points of Attack: Eyes, skin, respiratory system, liver, kidneys. Cancer site in animals: liver, uterus, pituitary gland. Medical Surveillance: Liver and kidney function tests. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Where there is potential for exposures over 10 mg/m3, use a NIOSH/MSHA- or European Standard EN149-approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full facepiece, hood, or helmet in the continuous-flow mode; or use a NIOSH/MSHA- or European Standard EN149-approved selfcontained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and
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Picolines
storage. Store in tightly closed containers in a cool, wellventilated area away from acids, bases, and metals. A regulated, marked area should be established where this chemical is handled, used, or stored. The use of picloram has been restricted. Be sure that your operation follows regulations. A regulated, marked area should be established where this chemical is handled, used, or stored in compliance with OSHA Standard 1910.1045. Shipping: Pesticides, solid, toxic, n.o.s. require a shipping label of “POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 6.1 and Packing Group III. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible solid. Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Poisonous gases are produced in fire, including hydrogen chloride and nitrogen oxides. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: This chlorinated brush killer is usually formulated with 2,4-D and the disposal problems are similar. Incineration at 1000 C for 2 s is required for thermal decomposition. Alternatively, the free acid can be precipitated from its solutions by addition of a mineral acid. The concentrated acid can then be incinerated and the dilute residual solution disposed in an area where several years’ persistence in the soil can be tolerated. References US Environmental Protection Agency. (August 1987). Health Advisory: Picloram. Washington, DC: Office of Drinking Water US Environmental Protection Agency, Special Review and Reregistration Division Office of Pesticide Programs. (1998). Agency Status of Pesticides in Registration,
Reregistration, and Special Review (Rainbow Report). Washington, DC New Jersey Department of Health and Senior Services. (May 2001). Hazardous Substances Fact Sheet: Picloram. Trenton, NJ
Picolines
P:0720
Molecular Formula: C6H7N Synonyms: 2-Picoline (o-isomer): AI3-2409; AI3-24109; α-Methylpyridine; 2-Methylpyridine; Metilpiridina (Spanish); NSC 3409; α-Picoline; o-Picoline; 2-Picoline; Picoline; Pyridine, 2-methyl-; Pyridine, methyl3-Picoline (m-isomer): β-Picoline; m-Picoline; β-Methylpyridine; m-Methylpyridine; 3-Methylpyridine; Pyridine, 3-methyl 4-Picoline (p-isomer): γ-Picoline; p-Picoline; γ-Methylpyridine; p-Methylpyridine; 4-Methylpyridine; Pyridine, 4-methyl CAS Registry Number: 109-06-8 (2-Picoline); 108-99-6 (3-Picoline); 108-89-4 (4-Picoline); 1333-41-1 (mixed isomers) RTECS® Number: TJ4900000 (2-Picoline); TJ5000000 (3-Picoline); UT5425000 (4-Picoline) UN/NA & ERG Number: UN2313/129 EC Number: 203-643-7 [Annex I Index No.: 613-036-00-2] (2-Picoline); 203-636-9 (3-Picoline); 203-626-4 [Annex I Index No.: 613-037-00-8] (4-Picoline); 215-588-6 (methylpyridine or mixed isomers) Regulatory Authority and Advisory Bodies (2-Picoline) Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. o-isomer: US EPA Hazardous Waste Number (RCRA No.): U191. RCRA, 40CFR261, Appendix 8 Hazardous Constituents. Reportable Quantity (RQ): 5000 lb (2270 kg). EPCRA Section 313 Form R de minimis concentration reporting level: 1.0%. Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations (2-picoline): Hazard Symbol: Xn; Risk phrases: R10; R20/21/22; R36/37; Safety phrases: S2; S26; S36; (4-picoline) Hazard Symbol: T; Risk phrases: R10; R20/22; R24; R36/37/38; Safety phrases: S1/ 2; S26; S36; S45 (see Appendix 4). WGK (German Aquatic Hazard Class): 1—Low hazard to waters (all isomers). Description: Picolines are colorless liquids with a strong, unpleasant, pyridine-like odor. Odor threshold is 0.023 ppm. “Picoline” is often used as mixed isomers and physical data for the other isomers are listed. The o-isomer is the most heavily regulated (see above). Molecular weight 5 93.14; Specific gravity (H2O:1) 5 0.96 at 25 C;
Picolines Boiling point 5 129 C (o-isomer); 143144 C (m-isomer); 145 C (p-isomer); Freezing/Melting point 5 70 C (o-isomer); 18 C (m-isomer); 3.7 C (p-isomer); Flash point 5 39 C (oc) (o-isomer); 37.8 C (cc) (m-isomer); 57 C (p-isomer); Autoignition temperature 5 535 C (o-isomer). Explosive limits (o-isomer): LEL 5 1.4%; UEL 5 8.6%. Hazard Identification (based on NFPA-704 M Rating System): (2-isomer) Health 3, Flammability 2, Reactivity 0; (3- and 4-isomers) Health 2, Flammability 2, Reactivity 0. Soluble in water. Potential Exposure: Compound Description (o-isomer): Mutagen, Primary Irritant; (m-isomer): Tumorigen, Primary Irritant. Picolines are used as intermediates in pharmaceutical manufacture, pesticide manufacture, and in the manufacture of dyes and rubber chemicals. It is also used as a solvent. Incompatibilities: Reacts with oxidants and strong acids. Attacks copper and its alloys. Permissible Exposure Limits in Air Protective Action Criteria (PAC) AIHA WEEL: 2 ppm, [skin] TWA; 5 ppm STEL (15 min) [skin], as picolines. 2-picoline TEEL-0: 2 ppm PAC-1: 5 ppm PAC-2: 5 ppm PAC-3: 300 ppm 3-picoline TEEL-0: 2 ppm PAC-1: 5 ppm PAC-2: 125 ppm PAC-3: 600 ppm Russia: 5 mg/m3.[43] (o-isomer) Permissible Concentration in Water: There are no US criteria but the maximum allowable concentration in Class I waters for the production of drinking water has been set in Russia at 0.05 mg/L.[43] The EPA has suggested[32] a permissible ambient goal of 316 μg/L based on health effects. Determination in Water: Octanolwater coefficient: Log Kow 5 1.2 (all isomers) Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Corrosive to the eyes, skin, and respiratory tract. Exposure can cause nausea, vomiting, diarrhea, and abdominal pain. Inhalation: May cause irritation to mouth, nose, and throat. Odor is very disagreeable above 30 ppm. However, people often become insensitive to the odor after a period of time, so odor detection cannot be relied upon as an indication of exposure. Exposure far above the OEL may cause you to pass out. Levels of 8000 ppm caused death in all exposed rats within 1.5 h. Skin: Readily absorbed and may contribute to symptoms. Irritation with rash or burning sensation on contact. May cause severe irritation if not promptly removed. Eyes: May cause severe irritation. Ingestion: Irritation and upset of
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digestive system may occur. Muscle weakness, loss of coordination, diarrhea, and unconsciousness may result. Animal studies suggest that death may occur by ingestion of 12 fluid ounces for a 150-lb person. Long Term Exposure: Repeated exposure to picoline can cause headache, dizziness, weakness, loss of coordination, double vision, and coma. Animal studies suggest that symptoms similar to those listed under ingestion would occur. Liver and kidney damage may also occur. Corrosive substances can irritate the lungs; bronchitis may develop. Points of Attack: Skin, eyes, liver and kidneys, lungs. Medical Surveillance: Liver and kidney function tests. Lung function tests. Consider chest X-ray following acute overexposure. Liver and kidney function tests. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Speed in removing material from skin is of extreme importance. Shampoo hair promptly if contaminated. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. A respirator providing protection against organic vapors may be of use to sensitive individuals and during entry or escape from a contaminated area. Storage: Color Code—Red: Flammability Hazard: Store in a flammable liquid storage area or approved cabinet away from ignition sources and corrosive and reactive materials.
2178
Picric acid
Prior to working with this chemical you should be trained on its proper handling and storage. Before entering confined space where this chemical may be present, check to make sure that an explosive concentration is not a danger. Store in tightly closed containers in a cool, well-ventilated area away from oxidizers, strong acids, acid chlorides, chloroformates, copper metals, and alloys. Where possible, automatically pump liquid from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of 5 gallons or more of this chemical should be grounded and bonded. Drums must be equipped with self-closing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: Picolines require a shipping label of “FLAMMABLE LIQUID.” They fall in DOT Hazard Class 3 and Packing Group II. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Establish forced ventilation to keep levels below explosive limit. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a flammable liquid. Poisonous gases, including nitrogen oxides, are produced in fire. Use dry chemical, carbon dioxide, or alcohol foam extinguishers. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained
breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. References US Environmental Protection Agency. (April 30, 1980). 2Picoline: Health and Environmental Effects Profile No. 148. Washington, DC: Office of Solid Waste New York State Department of Health. (March 1986). Chemical Fact Sheet: Picoline(s). Albany, NY: Bureau of Toxic Substance Assessment New Jersey Department of Health and Senior Services. (August, 1999). Hazardous Substances Fact Sheet: Picoline. Trenton, NJ
Picric acid
P:0730
Molecular Formula: C6H3N3O7 Common Formula: C6H2(NO2)3OH Synonyms: Acide picrique (French); Acido picrico (Spanish); Carbazotic acid; C.I. 10305; 2-Hydroxy-1,3,5-trinitrobenzene; Lyddite; Melinite; Nitroxanthic acid; PA; Pertite; Phenol trinitrate; Phenol, 2,4,6-trinitro-; Picral; Picronitric acid; Pikrinsaeure (German); Shimose; Trinitrophenol; Trinitrofenol (Spanish); 1,3,5Trinitrophenol; 2,4,6-Trinitophenol CAS Registry Number: 88-89-1 RTECS® Number: TJ7875000 UN/NA & ERG Number: UN0154 (dry or wetted with ,30% water, by mass)/112; UN3364 (wetted with not ,10% water, by mass)/113; UN1344 (wetted with not ,30% water, by mass)/113 EC Number: 201-865-9 [Annex I Index No.: 609-009-00-X] Regulatory Authority and Advisory Bodies Department of Homeland Security Screening Threshold Quantity (pounds): Release hazard 5000 (commercial grade); Theft hazard 400 (commercial grade). US EPA Gene-Tox Program, Inconclusive: D. melanogaster sex-linked lethal. An OSHA Class A Explosive (1910.109). Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. EPCRA Section 313 Form R de minimis concentration reporting level: 1.0%. Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: Hazard Symbol: E, T; R3; R4; R23/24/25; Safety phrases: S1/2; S28; S35; R36/ 37; R45 (see Appendix 4). WGK (German Aquatic Hazard Class): 2—Hazard to waters. Description: Picric acid is a pale yellow, odorless solid. Usually found in solution with 1020% water. Must be kept wetted; the crystalline form is highly unstable. The dry crystal form is explosive upon rapid heating or mechanical shock.
Picric acid Molecular weight 5 229.12; Specific gravity (H2O:1) 5 1.76 at 25 C; Boiling point 5 (explodes above 300 C); Freezing/ Melting point 5 122.2 C; Vapor pressure 5 1 mmHg at 25 C; Flash point 5 150 C; Autoignition temperature 5 (explodes) 300 C. Hazard Identification (based on NFPA704 M Rating System): Health 3, Flammability 4, Reactivity 4; (wet): Health 2, Flammability 2, Reactivity 2. Slightly soluble in water; solubility 5 1%. Potential Exposure: Compound Description: Mutagen. Picric acid is used in the synthesis of dye intermediates and in manufacturing picrates; in the manufacture of explosives, rocket fuels, fireworks, colored glass, matches, electric batteries, and disinfectants. It is also used in the pharmaceutical and leather industries, in copper and steel etching, forensic chemistry, histology, textile printing, and photographic emulsions. Incompatibilities: Violent reaction with oxidizers and reducing materials. Air or oxygen is not required for decomposition. Shock-sensitive compounds can be formed on contact with plaster, concrete. An explosive mixture results when the aqueous solution crystallizes. May explosively decompose from heat, shock, friction, or concussion. Copper, lead, zinc and other metals, or their salts can form other salts that are initiators and much more sensitive to shock than this chemical. Corrodes metals. Permissible Exposure Limits in Air Conversion factor: 1 ppm 5 9.37 mg/m3 at 25 C & 1 atm. OSHA PEL: 0.1 mg/m3 TWA [skin]. NIOSH REL: 0.1 mg/m3 TWA [skin]; 0.3 mg/m3 STEL. ACGIH TLV®[1]: 0.1 mg/m3 TWA. NIOSH IDLH: 75 mg/m3. Protective Action Criteria (PAC) TEEL-0: 0.1 mg/m3 PAC-1: 0.3 mg/m3 PAC-2: 15 mg/m3 PAC-3: 75 mg/m3 DFG MAK: 0.1 mg/m3, inhalable fraction; [skin] danger of skin sensitization; Carcinogen Category 3B. Australia: TWA 0.1 mg/m3; STEL 0.3 mg/m3, [skin], 1993; Austria: MAK 0.1 mg/m3, [skin], 1999; Belgium: TWA 0.1 mg/m3; STEL 0.3 mg/m3, [skin], 1993; Denmark: TWA 0.1 mg/m3, [skin], 1999; Finland: TWA 0.1 mg/m3; STEL 0.3 mg/m3, [skin], 1999; France: VME 0.1 mg/m3, [skin], 1999; Hungary: TWA 0.1 mg/m3; STEL 0.2 mg/m3, [skin], 1993; the Netherlands: MAC-TGG 0.1 mg/m3, [skin], 2003; Norway: TWA 0.1 mg/m3, 1999; the Philippines: TWA 0.1 mg/m3, [skin], 1993; Poland: MAC (TWA) 0.1 mg/m3; MAC (STEL) 0.3 mg/m3, 1999; Switzerland: MAK-W 0.1 mg/m3, KZG-W 0.2 mg/m3, [skin], 1999; Turkey: TWA 0.1 mg/m3, [skin], 1993; United Kingdom: TWA 0.1 mg/ m3; STEL 0.3 mg/m3, 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: TWA 0.1 mg/m3. Several states have set guidelines or standards for picric acid in ambient air[60] ranging from 0.33 μg/m3 (New York) to 1.0 μg/m3 (Florida, South Carolina) to 1.03.0 μg/m3 (North Dakota)
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to 1.6 μg/m3 (Virginia) to 2.0 μg/m3 (Connecticut and Nevada). Russia set a MAC of 10 μg/m3 for ambient air on a once-daily basis. Determination in Air: Collection on a mixed cellulose ester membrane filter, extraction with aqueous methanol measurement by high-performance liquid chromatography with UV detector. See NIOSH (II-4), Method #S-228. Permissible Concentration in Water: To protect human health: no criteria set due to insufficient data.[6] Russia[35, 43] set a MAC of 0.5 mg/L in water bodies used for domestic purposes. Determination in Water: Methylene chloride extraction followed by gas chromatography with flame ionization or electron capture detection (EPA Method 604) or gas chromatography plus mass spectrometry (EPA Method 625). Octanolwater coefficient: Log Kow 5 2.0. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Absorbed by the skin. Harmful Effects and Symptoms Short Term Exposure: LD50 5 (oral-rat) 200 mg/kg. Irritates the eyes, skin, and respiratory tract. Corneal injury may occur from exposure to picric acid dust and solutions. Dust or fume may cause eye irritation which may be aggravated by sensitization. Inhalation of high concentrations of dust by one worker caused temporary coma followed by weakness, myalgia, anuria, and later polyuria. Following ingestion of picric acid, there may be headache, vertigo, nausea, vomiting, diarrhea, yellow coloration of the skin, hematuria, and albuminuria. High doses may cause destruction of erythrocytes, hemorrhagic nephritis, and hepatitis. High doses which cause systemic intoxication will color all tissues yellow, including the conjunctive and aqueous humor, and cause yellow vision. Long Term Exposure: Picric acid dust or solutions are potent skin sensitizers. The cutaneous lesions which appear usually on exposed areas of the upper extremities consist of dermatitis with erythema and vesicular eruptions. Desquamation may occur following repeated or prolonged contact. Skin usually turns yellow upon contact, and areas around nose and mouth as well as the hair are most often affected. May cause liver effects, hepatitis, hematuria (blood in the urine), albuminuria, kidney effects, nephritis. Points of Attack: Eyes, skin, kidneys, liver, blood. Medical Surveillance: NIOSH lists the following tests: liver function tests; urinalysis (routine). Preplacement and periodic medical examinations should focus on skin disorders (such as hypersensitivity, atopic dermatitis) and liver and kidney function. Examination by a qualified allergist. Complete blood count (CBC). First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure,
2180
Picric acid
begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. Natural rubber, Neoprene™, and Nitrile are among the recommended protective materials. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash or dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Up to 0.5 mg/m3: Qm (APF 5 25) (any quarter-mask respirator). Up to 1 mg/m3): 95 XQ [any particulate respirator equipped with an N95, R95, or P95 filter (including N95, R95, and P95 filtering face-pieces) except quartermask respirators]. The following filters may also be used: N99, R99, P99, N100, R100, P100; or Sa (APF 5 10) (any suppliedair respirator). Up to 2.5 mg/m3: Sa:Cf (APF 5 25) (any supplied-air respirator operated in a continuous-flow mode) or PaprHie (APF 5 25) (any powered, air-purifying respirator with a high-efficiency particulate filter). Up to 5 mg/m3: 100F (APF 5 50) (any air-purifying, full-face-piece respirator with an N100, R100, or P100 filter) or SaT: Cf (APF 5 50) (any supplied-air respirator that has a tight-fitting face-piece and is operated in a continuous-flow mode) or PaprTHie (APF 5 50) (any powered, air-purifying respirator with a tight-fitting facepiece and a high-efficiency particulate filter) or SCBAF (APF 5 50) (any self-contained breathing apparatus with a full face-piece) or SaF (APF 5 50) (any supplied-air respirator with a full face-piece). Up to 75 mg/m3: SaF: Pd,Pp (APF 5 2000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd,Pp (APF 5 10,000) (any NIOSH/MSHA- or European Standard EN 149-approved self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode) or Sa: Pd,Pp (APF 5 1000): ASCBA (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary, self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: 100F (APF 5 50) (any air-purifying, full-face-piece respirator with an N100, R100, or P100 filter) or SCBAE (any appropriate escape-type, self-contained breathing apparatus). Storage: Explosive. Color Code—Red (wet): Flammability Hazard: Store in a flammable materials storage area. Prior to working with this chemical you should be trained on its
proper handling and storage. Store in an explosion-proof refrigerator away from oxidizers, reducing agents, and metals. Where possible, automatically pump liquid from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of 5 gallons or more of this chemical should be grounded and bonded. Drums must be equipped with self-closing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: Trinitrophenol or picric acid, dry or wetted with ,30% water, by mass, requires a shipping label of “EXPLOSIVES” It falls in Hazard Class 4.1. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Dampen spilled material with alcohol to avoid dust, then transfer material to a suitable container for eventual disposal. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a flammable solid. More powerful than TNT, picric acid explodes above 572 F/300 C. Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Poisonous gases are produced in fire, including nitrogen oxides. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. Containers may explode. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Controlled incineration in a rotary kiln incinerator equipped with particulate abatement and wet scrubber devices.[22] Reference US Environmental Protection Agency. (1980). Nitrophenols: Ambient Water Quality Criteria. Washington, DC
Picrotoxin
Picrotoxin
P:0740
Molecular Formula: C30H34O13 Synonyms: Cocculin; Cocculus; Coques du levant (French); Fish berry; Indian berry; Oriental berry; Picrotin, compounded with picrotoxinin (1:1); Picrotoxine CAS Registry Number: 124-87-8 RTECS® Number: TJ9100000 UN/NA & ERG Number: UN3172/153 EC Number: 204-716-6 Regulatory Authority and Advisory Bodies Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 500/10,000 lb (227/4540 kg). Reportable Quantity (RQ): 500 lb (227 kg). European/International Regulations: not listed in Annex 1. WGK (German Aquatic Hazard Class): No value assigned. Description: Picrotoxin is an odorless crystalline solid with a very bitter taste. Molecular weight 5 602.64; Freezing/ Melting point 5 203 C. Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 1, Reactivity 0. Practically insoluble in cold water; soluble in boiling water. Potential Exposure: An alkaloid poison and convulsant. Used in medicine as a central nervous system stimulant and antidote for barbiturate poisoning. Reportedly, this material is not currently regarded as a useful therapeutic agent since it is not a selective respiratory stimulant. Permissible Exposure Limits in Air Protective Action Criteria (PAC) TEEL-0: 3 mg/m3 PAC-1: 7.5 mg/m3 PAC-2: 15 mg/m3 PAC-3: 15 mg/m3 Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Highly toxic and a dose of 20 mg may produce symptoms of severe poisoning. A human lethal dose of 1.5 mg/kg has been reported. It is an alkaloid convulsant poison. Picrotoxin is a powerful stimulant and affects all portions of the central nervous system. At doses approaching convulsant levels, signs and symptoms include salivation, elevated blood pressure, frequent vomiting, rapid breathing. Points of Attack: Central nervous system. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical
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facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Keep victim quiet and maintain normal body temperature. Effects may be delayed; keep victim under observation. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, wellventilated area away. Where possible, automatically transfer material from drums or other storage containers to process containers. Shipping: Toxins, extracted from living sources, require a shipping label of “POISONOUS/TOXIC MATERIALS”. It falls in Hazard Class 6.1 and Packing Group I. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Stay upwind; keep out of low areas. Ventilate closed spaces before entering them. Remove and isolate contaminated clothing at the site. If water pollution occurs, notify appropriate authorities. Do not touch spilled material; stop leak if you can do it without risk. Use water spray to reduce vapors. Small spills: take up with sand or other noncombustible absorbent material and place into containers for later disposal. Small dry spills: with clean shovel place material into clean, dry container and cover; move containers from spill area. Large spills: dike far ahead of spill for later disposal. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly
2182
Pindone
trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: Use dry chemical, carbon dioxide, water spray, or foam for small fires. Use water spray, fog, or foam for large fires. Move container from fire area if this can be done without risk. Isolate hazard area and deny entry. Wear positive pressure breathing apparatus and special protective clothing. Poisonous gases are produced in fire. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Reference US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Picrotoxin. Washington, DC: Chemical Emergency Preparedness Program
Pindone
P:0760
Molecular Formula: C14H14O3 Common Formula: C6H4(CO)2CHCOC(CH3)3 Synonyms: Chemrat; tert-Butyl valone; 1,3-Dioxo-2-pivaloy-lindane; Pival®; Pivalyl; 2-Pivalyl-1,3-indandione; Pivalyl Valone®; Pivaldione (French) CAS Registry Number: 83-26-1 RTECS® Number: NK6300000 UN/NA & ERG Number: UN2588/151 EC Number: 201-462-8 [Annex I Index No.: 606-016-00-X] Regulatory Authority and Advisory Bodies US EPA, FIFRA 1998 Status of Pesticides: RED completed. Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. European/International Regulations: Hazard Symbol: T, N; Risk phrases: R25 R48/25;R50/53; Safety phrases: S1/2; S37; S45; S60; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): No value assigned. Description: Pindone is a bright yellow crystalline solid. Almost odorless. Molecular weight 5 230.28; Specific gravity (H2O:1) 5 1.06 at 25 C; Boiling point 5 decomposes; Freezing/Melting point 5 110 C. Practically insoluble in water; solubility 5 0.002% at 25 C. Potential Exposure: Compound Description: Agricultural Chemical. Pindone is used as an anticoagulant and rodenticide. Those involved in manufacture, formulation, and application of this chemical.
Incompatibilities: None reported. Permissible Exposure Limits in Air OSHA PEL: 0.1 mg/m3 TWA. NIOSH REL: 0.1 mg/m3 TWA. ACGIH TLV®[1]: 0.1 mg/m3 TWA. NIOSH IDLH: 100 mg/m3. No TEEL available. Australia: TWA 0.1 mg/m3, 1993; Belgium: TWA 0.1 mg/m3, 1993; Denmark: TWA 0.1 mg/m3, 1999; France: VME 0.1 mg/m3, 1999; Norway: TWA 0.1 mg/m3, 1999; Switzerland: MAK-W 0.1 mg/m3, 1999; the Netherlands: MAC-TGG 0.1 mg/m3, 2003; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: TWA 0.1 mg/m3. Several states have set guidelines or standards for pindone in ambient air[60] ranging from 1.03.0 μg/m3 (North Dakota) to 1.6 μg/m3 (Virginia) to 2.0 μg/m3 (Connecticut and Nevada). Determination in Air: No method available. Routes of Entry: Inhalation, ingestion. Harmful Effects and Symptoms Short Term Exposure: Nosebleeds (epistaxis), excessive bleeding of minor cuts and bruises, smoky urine, black tarry stools, abdominal and back pain. Reduced blood clotting which leads to hemorrhaging; symptoms resembling warfarin: depressed formation of prothrombin and capillary fragility; leading to hemorrhages. Points of Attack: Blood prothrombin. Medical Surveillance: NIOSH lists the following tests: blood plasma, Prothrombin Time; Complete blood count; urinalysis (routine), red blood cells/count. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash.
Piperazine Respirator Selection: Up to 0.5 mg/m3: Qm (APF 5 25) (any quarter-mask respirator). Up to 1 mg/m3): 95XQ (APF 5 10) [any particulate respirator equipped with an N95, R95, or P95 filter (including N95, R95, and P95 filtering face-pieces) except quarter-mask respirators. The following filters may also be used: N99, R99, P99, N100, R100, P100] or Sa (APF 5 10) (any supplied-air respirator). Up to 2.5 mg/m3: Sa:Cf (APF 5 25) (any supplied-air respirator operated in a continuous-flow mode) or PaprHie (APF 5 25) (any powered, air-purifying respirator with a high-efficiency particulate filter). Up to 5 mg/m3: 100F (APF 5 50) (any air-purifying, full-face-piece respirator with an N100, R100, or P100 filter) or SaT: Cf (APF 5 50) (any supplied-air respirator that has a tightfitting face-piece and is operated in a continuousflow mode) or PaprTHie (APF 5 50) (any powered, air-purifying respirator with a tight-fitting face-piece and a high-efficiency particulate filter) or SCBAF (APF 5 50) (any self-contained breathing apparatus with a full facepiece) or SaF (APF 5 50) (any supplied-air respirator with a full face-piece). Up to 100 mg/m3: Sa: Pd,Pp (APF 5 1000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd, Pp (APF 5 10,000) (any NIOSH/MSHA- or European Standard EN 149-approved self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode) or SaF: Pd, Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressuredemand or other positive-pressure mode in combination with an auxiliary, self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: 100F (APF 5 50) (any air-purifying, fullface-piece respirator with an N100, R100, or P100 filter) or SCBAE (any appropriate escape-type, self-contained breathing apparatus). Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in a refrigerator or a cool, dry place. Shipping: Pesticides, solid, toxic, n.o.s. require a shipping label of “POISONOUS/TOXIC MATERIALS.” (Packing Group III): It falls in Hazard Class 6.1 and Packing Group III. Spill Handling: Remove all sources of ignition and dampen spilled material with 6070% ethanol to avoid airborne dust, then transfer material to a suitable container. Wash surfaces well with soap and water. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up
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spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Poisonous gases are produced in fire. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosionproof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Dissolve or mix the material with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber. All federal, state, and local environmental regulations must be observed.[22] In accordance with 40CFR165, follow recommendations for the disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by contacting your local or federal environmental control agency or by contacting your regional EPA office. Reference US Environmental Protection Agency, Special Review and Reregistration Division Office of Pesticide Programs. (1998). Agency Status of Pesticides in Registration, Reregistration, and Special Review (Rainbow Report). Washington, DC
Piperazine
P:0770
Molecular Formula: C4H10N2; C4H12Cl2N2 Common Formula: C4H10N2 2HCl; C4H10N2 HCl (monochloride) Synonyms: Antiren; N,N-Diethylene diamine; 1,4Diethylenediamine; Dihydrochloride salt of diethylenediamine; Dispermine; Dowzene; Hexahydro-1,4-diazine; Hexahydropyrazine; Lumbrical; Piperazidine; Piperazin (German); Piperazine dihydrochloride; Piperazine hydrochloride; Pyrazine hexahydride CAS Registry Number: 110-85-0; 142-64-3 (hydrochloride) RTECS® Number: TL4025000 (hydrochloride); TK7800000 UN/NA & ERG Number: UN2579/153 EC Number: 203-808-3 [Annex I Index No.: 612-057-004]; 205-551-2 [Annex I Index No.: 612-241-00-4] (hydrochloride) Regulatory Authority and Advisory Bodies Banned or Severely Restricted (several countries) (UN).[13] Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section.
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Piperazine
Canada, WHMIS, Ingredients Disclosure List Concentration) 0.1% (Piperazine and Piperazine dihydrochloride). European/International Regulations: Hazard Symbol: Xn, C; Risk phrases: R34; R42/43; R62; R63; Safety phrases: S1/2; S22; S26; S36/37/39; S45; (hydrochloride): Hazard Symbol: Xn, C, N; Risk phrases: R36/38; R42/43; R62; R63; R52/53; Safety phrases: S1/2; S22; S36/37; S45; S61; S63 (see Appendix 4). WGK (German Aquatic Hazard Class): 1—Low hazard to waters. Description: Piperazine and Piperazine dihydrochloride, are white to cream-colored needles or powder with a characteristic ammonia-like odor. Combustible solids that do not easily ignite. Molecular weight 5 86.16 (piperazine); 159.08 (dihydrochloride); Boiling point 5 146 C; Freezing/Melting point 5 106 C; 335 C (dihydrochloride); Flash point 5 110 C. Hazard Identification (based on NFPA-704 M Rating System): (piperazine) Health 2, Flammability 2, Reactivity 0. Soluble in water. Potential Exposure: Compound Description (Piperazine): Agricultural Chemical; Drug, Human Data; Primary Irritant; (dihydrochloride) Agricultural Chemical; Mutagen. Piperazine is used to manufacture anthelmintics, antifilarials, antihistamines, and tranquilizers; the dihydrochloride is used in the manufacture of fibers, pharmaceuticals, and insecticides. They are used as an intermediate in the manufacture of pesticides, rubber chemicals, and fibers. Also, piperazine is widely available, effective, and safe when used on an occasional basis against ascaride infections. It is also considerably cheaper than other anthelminthic drugs. In some countries where ascariasis is not endemic and where piperazine was used predominantly for the treatment of pinworn, it has been withdrawn from use on the grounds that other effective drugs are now available. Clinical dosages occasionally induce transient neurological signs and, in some circumstances, the drug may generate small amounts of nitrosamine in the stomach, which at considerably greater dosage in experimental animals has been demonstrated to have a carcinogenic potential. Incompatibilities: Violent reaction with strong oxidizers and dicyanofurazan. Incompatible with nitrogen compounds, carbon tetrachloride. Attacks aluminum, copper, nickel, magnesium, and zinc. Permissible Exposure Limits in Air ACGIH TLV (piperazine and piperazine dihydrochloride): 2010 Notice of intended change: 0.1 mg/m3 measured as inhalable fraction and vapor TWA; Danger of sensitization; not classifiable as a human carcinogen. NIOSH REL (dihydrochloride): 5 mg/m3 TWA. Piperazine Protective Action Criteria (PAC) TEEL-0: 2 mg/m3 PAC-1: 6 mg/m3 PAC-2: 40 mg/m3 PAC-3: 500 mg/m3
DFG MAK (piperazine): Danger of skin and airway sensitization. Denmark: TWA 0.1 ppm (0.35 mg/m3), 1999; Norway: TWA 0.1 ppm (0.3 mg/m3), 1999; Sweden: NGV 0.1 ppm (0.3 mg/m3), KTV 0.3 ppm (1 mg/m3), 1999; the Netherlands: MAC-TGG 0.1 mg/m3, 2003. Dihydrochloride OSHA PEL: None. NIOSH REL: 5 mg/m3 TWA. ACGIH TLV®[1]: 5 mg/m3 TWA. DFG MAK: Danger of skin and airway sensitization; No numerical value established. Data may be available. Australia: TWA 5 mg/m3, 1993; Belgium: TWA 5 mg/m3, 1993; Denmark: TWA 5 mg/m3, 1999; France: VME 5 mg/ m3, 1999; Switzerland: MAK-W 5 mg/m3, 1999; United Kingdom: TWA 5 mg/m3, 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: TWA 5 mg/m3, 2003. Determination in Air: No method available. Routes of Entry: Inhalation, skin absorption, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Piperazine can affect you when breathed in and by passing through your skin. Piperazine is a corrosive chemical and eye contact can cause severe irritation and burns. Skin contact can cause irritation or a skin allergy, with rash at even very low exposure levels. Exposure can cause a lung allergy to develop, with cough and wheezing triggered by even low exposures. Higher exposures can cause pulmonary edema, a medical emergency that can be delayed for several hours. This can cause death. High exposures can cause weakness, tremors, visual changes, and trigger seizures. It can also interfere with the ability of the blood to carry oxygen, causing headaches, dizziness, and cyanosis, a bluish color to the skin and lips. Long Term Exposure: Repeated exposure to piperazine dihydrochloride can cause skin sensitization and asthmalike allergy. Points of Attack: Lungs. Medical Surveillance: If symptoms develop or overexposure is suspected, the following may be useful: evaluation by a qualified allergist, including careful exposure history and special testing, may help diagnose skin allergy. Lung function tests. These may be normal if the person is not having an attack at the time of the test. Blood methemoglobin level. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical
Piperidine facility. When this chemical has been swallowed, get medical attention. If victim is conscious, administer water or milk. Do not induce vomiting. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. Note to physician: Treat for methemoglobinemia. Spectrophotometry may be required for precise determination of levels of methemoglobin in urine. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Where there is potential for exposures over 5 mg/m3, use a NIOSH/MSHA- or European Standard EN149-approved full-face-piece respirator with a high-efficiency particulate filter. Greater protection is provided by a powered air-purifying respirator. Where there is potential for high exposures, use a NIOSH/MSHA- or European Standard EN149-approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuous-flow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—White: Corrosive or Contact Hazard; Store separately in a corrosion-resistant location. Prior to working with this chemical you should be trained on its proper handling and storage. Piperazine must be stored to avoid contact with oxidizers (such as perchlorates, peroxides, permanganates, chlorates, and nitrates) since violent reactions occur. Sources of ignition, such as smoking and open flames, are prohibited where piperazine is used, handled, or stored in a manner that could create a potential fire or explosion hazard. Store in tightly closed containers in a cool, well-ventilated area. Where possible, automatically transfer material from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of this chemical should be grounded and bonded. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: Piperazine requires a shipping label of “CORROSIVE.” It falls in Hazard Class 8 and Packing Group III.
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Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: Piperazine is a combustible solid. Use dry chemical, water spray, or alcohol foam extinguishers. Piperazine dihydrochloride may burn but does not readily ignite. Extinguish fire using an agent suitable for type of surrounding fire. Poisonous gases, including nitrogen oxides and hydrogen chloride (hydrochloride), are produced in fire. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. References New Jersey Department of Health and Senior Services. (September 2004). Hazardous Substances Fact Sheet: Piperazine Dihydrochloride. Trenton, NJ New Jersey Department of Health and Senior Services. (April 2004). Hazardous Substances Fact Sheet: Piperazine. Trenton, NJ
Piperidine
P:0780
Molecular Formula: C5H11N Synonyms: Azacyclohexane; Cyclopentimine; Cypentil; Hexahydropyridine; Hexazane; Pentamethyleneimine; Peperidin (German) CAS Registry Number: 110-89-4 RTECS® Number: TM3500000 UN/NA & ERG Number: UN2401/132 EC Number: 203-813-0 [Annex I Index No.: 613-027-00-3] Regulatory Authority and Advisory Bodies Department of Homeland Security Screening Threshold Quantity (pounds): Release hazard 10,000 ($1.00% concentration).
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Piperidine
Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Clean Air Act: Accidental Release Prevention/Flammable Substances, (Section 112[r], Table 3), TQ 5 15,000 lb (6810 kg). Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 1000 lb (454 kg). Reportable Quantity (RQ): 1000 lb (454 kg). European/International Regulations: Hazard Symbol: F, T; Risk phrases: R11; R23/24; R34; Safety phrases: S1/2; S16; S26; S27; S45 (see Appendix 4). WGK (German Aquatic Hazard Class): No value assigned. Description: Piperidine is a clear, colorless liquid with an amine-like odor. Molecular weight 5 85.17; Boiling point 5 106 C; Freezing/Melting point 5 7 C; Flash point 5 16 C. Soluble in water. Potential Exposure: Compound Description: Mutagen; Reproductive Effector; Primary Irritant. Piperidine is used in agriculture and pharmaceuticals; as an intermediate for rubber accelerators; as a solvent; as a curing agent for rubber and epoxy resins; catalyst for condensation reactions; as an ingredient in oils and fuels; as a complexing agent; in the manufacture of local anesthetics; in analgesics; pharmaceuticals, wetting agents; and germicides; in synthetic flavoring. Not registered as a pesticide in the United States. Incompatibilities: Piperidine is a medium strong base. Reacts violently with oxidizers. Permissible Exposure Limits in Air AIHA WEEL: 1 ppm TWA [skin]. Protective Action Criteria (PAC)* TEEL-0: 1 ppm PAC-1: 6.6 ppm PAC-2: 33 ppm PAC-3: 110 ppm *AEGLs (Acute Emergency Guideline Levels) & ERPGs (Emergency Response Planning Guideline) are in bold face. United Kingdom: TWA 1 ppm/3.5 mg/m3 [skin]. Russia[43] MAC (work-place air) 0.2 mg/m3. Permissible Concentration in Water: Russia[43] set a MAC of 0.06 mg/L in water bodies used for domestic purposes. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Corrosive to the eyes, skin, and respiratory tract. Sore throat, coughing, labored breathing, and dizziness occur after inhalation. Higher exposures can cause pulmonary edema, a medical emergency that can be delayed for several hours. This can cause death. Exposure may cause increased blood pressure. May cause permanent injury after short exposure to small amounts. Ingestion may involve both irreversible and reversible changes. 3060 mg/kg may cause symptoms in humans. Symptoms upon oral administration include weakness, nausea, vomiting, salivation, labored respiration, muscular paralysis, and asphyxiation. Redness, pain, and burns occur upon contact with skin.
Long Term Exposure: Irritating substances may cause lung irritation; bronchitis may develop. May affect the liver and kidneys. Points of Attack: Lungs, blood, liver, kidneys. Medical Surveillance: Monitor blood pressure. Lung function tests. Liver and kidney function tests. Consider chest X-ray following acute overexposure. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—Red: Flammability Hazard: Store in a flammable liquid storage area or approved cabinet away from ignition sources and corrosive and reactive materials. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, well-ventilated area away from oxidizers. Where possible, automatically pump liquid from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are
Pirimifos-ethyl prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of 5 gallons or more of this chemical should be grounded and bonded. Drums must be equipped with self-closing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: Piperidine requires a shipping label of “FLAMMABLE LIQUID, CORROSIVE.” It falls in Hazard Class 3 and Packing Group II. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Shut off ignition sources; no flares, smoking, or flames in hazard area. Do not touch spilled material; stop leak if you can do so without risk. Use water spray to reduce vapors; do not get water inside container. Small spills: absorb with sand or other noncombustible absorbent material and place into containers for later disposal. Large spills: dike far ahead of spill for later disposal. Ventilate area of spill or leak. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a flammable liquid. Small fires: dry chemical, carbon dioxide, water spray, or alcohol foam. Large fires: water spray, fog, or alcohol foam. Move container from fire area if you can do it without risk. Do not get water inside container. Cool containers that are exposed to flames with water from the side until well after fire is out. Withdraw immediately in case of rising sound from venting safety device or any discoloration of tank due to fire. Keep unnecessary people away; isolate hazard area and deny entry. Stay upwind; keep out of low area. Wear self-contained (positive pressure if available) breathing apparatus and full protective clothing. Isolate for 1 /2 mile in all directions if tank car or truck is involved in fire. Poisonous gases, including nitrogen oxides, are produced in fire. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire
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officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. References US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Piperidine. Washington, DC: Chemical Emergency Preparedness Program New Jersey Department of Health and Senior Services. (September, 1999). Hazardous Substances Fact Sheet: Piperidine. Trenton, NJ
Pirimifos-ethyl
P:0790
Molecular Formula: C13H24N3O3PS Synonyms: O-[2-(Diethylamino)-6-methyl-4-pyrimidinyl] O,O-diethyl phosphorothioate; 2-Diethylamino-6-methylpyrimidin-4-yl diethylphosphorothionate; O,O-Diethyl O(2-diethylamino-6-methyl-4-pyrimidinyl) phosphorothioate; Diethyl O-(2-diethylamino-6-methyl-4-pyrimidinyl) phosphorothioate; Diethyl 2-dimethylamino-4-methylpyrimidin6-yl phosphorothionate; Ethyl pirimiphos; Fernex; Phosphorothioic acid, O-[2-(diethylamino)-6-methyl-4-pyrimidinyl] O,O-diethyl ester; PP211; Primicid; Primifosethyl; Primotec; Prinicid; R 42211; Solgard CAS Registry Number: 23505-41-1 RTECS® Number: TF1610000 UN/NA & ERG Number: UN3278 (organophosphorus compound, toxic n.o.s.)/151 EC Number: 245-704-0 [Annex I Index No.: 015-099-00-6] Regulatory Authority and Advisory Bodies Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 1000 lb (454 kg). Reportable Quantity (RQ): 1000 lb (454 kg). US DOT Regulated Marine Pollutant (49CFR172.101, Appendix B), severe pollutant. US DOT 49CFR172.101, Inhalation Hazard Chemical as organophosphates. European/International Regulations: Hazard Symbol: T, N; Risk phrases: R21; R25; R50/53; Safety phrases: S1/2; S23; S36/37; S45S; S60; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): No value assigned. Description: Pirimifos-ethyl is a straw-colored liquid. Molecular weight 5 333.43; It decomposes at 130 C; no boiling point can be determined; Vapor pressure 5 0.0003 mmHg. Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 1, Reactivity 1. Decomposes in water.
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Pirimifos-ethyl
Potential Exposure: Those involved in the manufacture, formulation, and application of this organophosphate soil insecticide. Permissible Exposure Limits in Air Protective Action Criteria (PAC) TEEL-0: 5 mg/m3 PAC-1: 15 mg/m3 PAC-2: 25 mg/m3 PAC-3: 60 mg/m3 Determination in Water: Fish Tox 5 1.70268000 ppb MATC (HIGH) Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Absorbed through the skin. Harmful Effects and Symptoms Short Term Exposure: As with other organophosphorus pesticides, symptoms are secondary to cholinesterase inhibition: headache, giddiness, blurred vision, nervousness, weakness, nausea, cramps, diarrhea, and discomfort in the chest. Other signs include sweating, tearing, salivation, vomiting, cyanosis, convulsions, coma, loss of reflexes, and loss of sphincter control. Long Term Exposure: Cholinesterase inhibitor; cumulative effect is possible. This chemical may damage the nervous system with repeated exposure, resulting in convulsions, respiratory failure. May cause liver damage. Human Tox; 1.40000 ppb (HIGH). Points of Attack: Respiratory system, lungs, central nervous system, cardiovascular system, skin, eyes, plasma and red blood cell cholinesterase. Medical Surveillance: Before employment and at regular times after that, the following are recommended: plasma and red blood cell cholinesterase levels (tests for the enzyme poisoned by this chemical). If exposure stops, plasma levels return to normal in 12 weeks while red blood cell levels may be reduced for 13 months. When cholinesterase enzyme levels are reduced by 25% or more below preemployment levels, risk of poisoning is increased, even if results are in lower ranges of “normal.” Reassignment to work not involving organophosphate or carbamate pesticides is recommended until enzyme levels recover. If symptoms develop or overexposure occurs, repeat the above tests as soon as possible and get an examination of the nervous system. Also, consider complete blood count. Consider chest X-ray following acute overexposure. Do not drink any alcoholic beverages before or during use. Alcohol promotes absorption of organic phosphates. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Speed in removing material from skin is of extreme importance. Shampoo hair promptly if contaminated. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin
rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, wellventilated area away from oxidizers. Where possible, automatically pump liquid from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of 5 gallons or more of this chemical should be grounded and bonded. Drums must be equipped with selfclosing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: This compound requires a shipping label of “POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 6.1 and Packing Group III. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. As with other organophosphorus pesticides, stay upwind; keep out of low areas. Ventilate closed spaces before entering them. Do not touch spilled material; stop leak if you can do so without risk. Use water spray to reduce vapors. Small spills: absorb with sand or other noncombustible absorbent material and place into containers for later disposal. Large spills: dike far ahead of spill for
Platinum and compounds later disposal. Remove all ignition sources. Ventilate area of spill or leak. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Initial isolation and protective action distances: Distances shown are likely to be affected during the first 30 min after materials are spilled and could increase with time. If more than one tank car, cargo tank, portable tank, or large cylinder involved in the incident is leaking, the protective action distance may need to be increased. You may need to seek emergency information from CHEMTREC at (800) 4249300 or seek professional environmental engineering assistance from the US EPA Environmental Response Team at (908) 548-8730 (24-h response line). Small spills (From a small package or a small leak from a large package) First: Isolate in all directions (feet/meters) 100/30 Then: Protect persons downwind (miles/kilometers) Day 0.3/0.4 Night 0.8/1.2 Large spills (From a large package or from many small packages) First: Isolate in all directions (feet/meters) 600/200 Then: Protect persons downwind (miles/kilometers) Day 1.6/2.6 Night 2.8/4.5 Fire Extinguishing: This material may burn but does not ignite readily. For small fires, use dry chemical, carbon dioxide, water spray, or foam. For large fires, use water spray, fog, or foam. Stay upwind; keep out of low areas. Move containers from fire area if you can do it without risk. Fight fire from maximum distance. Dike fire control water for later disposal; do not scatter the material. Poisonous gases, including nitrogen oxide, phosphorus oxides, and sulfur oxides, are produced in fire. Vapors are heavier than air and will collect in low areas. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and
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equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: In accordance with 40CFR165, follow recommendations for the disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by contacting your local or federal environmental control agency or by contacting your regional EPA office. References US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: PirimiphosEthyl. Washington, DC: Chemical Emergency Preparedness Program
Platinum and compounds
P:0800
Molecular Formula: Pt Synonyms: Elemental platinum; Platin (German); Platinum black CAS Registry Number: 7440-06-4 (Platinum metal); 16941-12-1 (Chloroplatinic acid); 10025-65-7 (Platinous chloride); 13454-96-1 [Platinum(IV) chloride]; 592-06-3 (Platinum cyanide) RTECS® Number: TP2160000 (Platinum metal); FW7040000 (Chloroplatinic acid); TP2275000 (Platinous chloride); TP2275500 (Platinum(IV) chloride) UN/NA & ERG Number: Metal powder, in bulk, may be pyrophoric: UN2545 (powder, dry)/135; UN2507 (chloroplatinic acid)/ 154 EC Number: 231-116-1 (platinum) Regulatory Authority and Advisory Bodies Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. Carcinogenicity (Platinum(IV) chloride): EPA Gene-Tox Program, Positive: B. subtilis rec assay; D. melanogaster sex-linked lethal. WGK (German Aquatic Hazard Class): Nonwater polluting agent. (metal) Description: Platinum is a soft, ductile, malleable, silverwhite metal. It is found in the metallic form and as the arsenide, sperrylite. It forms complex soluble salts, such as Na2PtCl6. It also forms halides. Metallic platinum is insoluble in water. Platinum(IV) chloride is red-brown crystals or powder. Molecular weight 5 195.09; 336.89 [Platinum(IV) chloride] Freezing/Melting point 5 (decomposes) 370 C. Soluble in water. Potential Exposure: Compound Description (metal): Drug, Tumorigen, (platinum(IV) chloride) Mutagen; Reproductive Effector; Primary Irritant. Platinum and its alloys are utilized because of their resistance to corrosion and oxidation,
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Platinum and compounds
particularly at high temperatures; their high electrical conductivity; and their excellent catalytic properties. They are used in relays, contacts and tubes in electronic equipment, in spark plug electrodes for aircraft, and windings in hightemperature electrical furnaces. Platinum alloys are used for standards for weight, length, and temperature measurement. Platinum and platinum catalysts (e.g., hexachloroplatinic acid, H2PtCl6) are widely used in the chemical industry in persulfuric, nitric, and sulfuric acid production, in the synthesis of organic compounds and vitamins, and for producing higher octane gasoline. They are coming into use in catalyst systems for control of exhaust pollutants from automobiles. They are used in the equipment for handling molten glass and manufacturing fibrous glass; in laboratory, medical, and dental apparatus; in electroplating; in photography; in jewelry; and in X-ray fluorescent screens. Because platinum complexes are used as antitumor agents, the potential for carcinogenic activity is present; tests to clarify this aspect should be conducted. While low levels of emissions of platinum particulate have been observed from some catalyst-equipped automobiles, the major potential source of Pt is from the disposal of spent catalysts. Incompatibilities: Platinum metal is incompatible with aluminum, acetone, arsenic, ethane, hydrazine, hydrogen peroxide, lithium, phosphorus, selenium, tellurium, various fluorides. Platinum(IV) chloride and finely divided powders are incompatible with oxidizers. Permissible Exposure Limits in Air OSHA PEL (soluble salts, as Pt) 0.002 mg[Pt]/m3 TWA. NIOSH REL (metal): 1 mg/m3; (soluble salts, as Pt): 0.002 mg[Pt]/m3 TWA. ACGIH TLV®[1] (soluble salts, as Pt): 1 mg/m3 (metal); 0.002 mg[Pt]/m3 TWA. NIOSH IDLH: 4 mg [Pt]/m3. Protective Action Criteria (PAC) TEEL-0: 1 mg/m3 PAC-1: 3 mg/m3 PAC-2: 4 mg/m3 PAC-3: 4 mg/m3 DFG MAK (chloroplatinates): 0.002 mg[Pt]/m3 Ceiling Concentration (peak should not be exceeded); danger of skin and airway sensitization. Protective Action Criteria (PAC) 16941-12-1, Dihydrogen hexachloroplatinate. TEEL-0: 0.0042 mg/m3 PAC-1: 0.25 mg/m3 PAC-2: 1.5 mg/m3 PAC-3: 8.4 mg/m3 Australia: TWA 1 mg/m3, 1993; Austria: MAK 1 mg/m3, 1999; Belgium: TWA 1 mg/m3, 1993; Finland: TWA 1 mg/m3, 1999; France: VME 1 mg/m3, 1999; Hungary: TWA 0.001 mg/m3; STEL 0.002 mg/m3, 1993; Norway: TWA 0.002 mg/m3, 1999; the Netherlands: MAC-TGG 1 mg/m3, 2003; Switzerland: MAK-W 0.002 mg[Pt]/m3, 1999; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: TWA
1 mg/m3. Several states have set guidelines or standards for platinum in ambient air[60] ranging from 0.1 μg/m3 (Nevada) to 0.420.0 μg/m3 (Connecticut) to 10.0 μg/m3 (North Dakota) to 330.0 μg/m3 (Virginia). Platinum(IV)chloride Arab Republic of Egypt: TWA 0.002 mg[Pt]/m3 (dust), 1993; Australia: TWA 0.002 mg[Pt]/m3, 1993; Austria: MAK 0.002 mg[Pt]/m3, 1999; Belgium: TWA 0.002 mg [Pt]/m3, 1993; Hungary: STEL 0.002 mg[Pt]/m3, 1993; Norway: TWA 0.002 mg[Pt]/m3, 1999; the Philippines: TWA 0.002 mg[Pt]/m3, 1993; Switzerland: MAK-W 0.002 mg[Pt]/m3, 1999; United Kingdom: LTEL 0.002 mg [Pt]/m3, 1993; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: TWA 0.002 mg[Pt]/m3 Platinum cyanide Protective Action Criteria (PAC) TEEL-0: 0.00253 mg/m3 PAC-1: 0.0076 mg/m3 PAC-2: 0.0127 mg/m3 PAC-3: 5.07 mg/m3 Determination in Air: Use NIOSH Analytical Method (IV) #7300, #7303, Elements by ICP; #8310, Metals in urine; #8005, Elements in blood or tissue, OSHA Analytical Method ID-121; ID-130-SG; NIOSH II(7), Method S-19, Soluble salts. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Metal dust and fume may cause irritation of the eyes, skin, and respiratory tract. Metal particles in the eye can cause scratching and possible damage. Hazards arise from the dust, droplets, spray, or mist of complex salts of platinum but not from the metal itself. These salts are sensitizers of the skin, nasal mucosa, and bronchi, and cause allergic phenomena. One case of contact dermatitis from wearing a ring made of platinum alloy is recorded. Long Term Exposure: Characteristic symptoms of poisoning occur after 26 months of exposure and include pronounced irritation of the throat and nasal passages, which results in violent sneezing and coughing; bronchial irritation, which causes respiratory distress; and irritation of the skin, which produces cracking, bleeding, and pain. Respiratory symptoms can be so severe that exposed individuals may develop status asthmaticus. After recovery, most individuals develop allergic symptoms and experience further asthma attacks when exposed to even minimal amounts of platinum dust or mists. Mild cases of dermatitis involve only erythema and urticaria of the hands and forearms. More severe cases affect the face and neck. All pathology is limited to allergic manifestations. EPA research efforts indicate that platinum is more active biologically and toxicologically than previously believed. It methylates in aqueous media, establishing a previously unrecognized biotransformation and distribution mechanism. Points of Attack: Respiratory system, skin, eyes.
Platinum and compounds Medical Surveillance: NIOSH lists the following tests: whole blood (chemical/metabolite); biologic tissue/biopsy; urine (chemical/metabolite). In preemployment and periodic physical examinations, the skin, eyes, and respiratory tract are most important. Any history of skin or pulmonary allergy should be noted, as well as exposure to other irritants or allergens, and smoking history. Periodic assessment of pulmonary function may be useful. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When chloroplatinic acid has been swallowed, get medical attention. If victim is conscious, administer water or milk. Do not induce vomiting. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear appropriate splash- or dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: (for soluble Pt salts): Up to 0.05 mg/m3: Sa:Cf* (APF 5 25) (any supplied-air respirator operated in a continuous-flow mode). Up to 0.1 mg/m3: 100F (APF 5 50) (any air-purifying, full-face-piece respirator with an N100, R100, or P100 filter) or SCBAF (APF 5 50) (any self-contained breathing apparatus with a full face-piece) or SaF (APF 5 50) (any supplied-air respirator with a full face-piece). Up to 4 mg/m3: SaF: Pd,Pp (APF 5 2000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd, Pp (APF 5 10,000) (any NIOSH/MSHA- or European Standard EN 149-approved self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode) or SaF: Pd, Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressuredemand or other positive-pressure mode in combination with an auxiliary, self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: 100 F (APF 5 50) (any air-purifying,
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full-face-piece respirator with an N100, R100, or P100 filter) or SCBAE (any appropriate escape-type, self-contained breathing apparatus). *Substance causes eye iritation and damage; eye protection needed. Storage: Color Code—White (chloroplatinic acid): Corrosive or Contact Hazard; Store separately in a corrosion-resistant location. Prior to working with this chemical you should be trained on its proper handling and storage. Shipping: Chloroplatinic acid, solid, is the only soluble salt cited. This compound requires a shipping label of “CORROSIVE.” It falls in Hazard Class 8 and Packing Group III. Fulminating platinum is also cited. Its Hazard class is “FORBIDDEN.” Dry powder, in bulk, requires a shipping label of “SPONTANEOUSLY COMBUSTIBLE.” It falls in Hazard Class 4.2 and Packing Group II. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible solid. Use dry chemicals appropriate for metal fires. Do not use water. Poisonous gases are produced in fire, including Pt. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positivepressure mode. Disposal Method Suggested: Catalyst disposal is expected to be the largest contributor of Pt to the environment. The value of the metal would help to offset the cost of reclaiming the Pt from discarded catalysts. If direct vehicular emissions of Pt are found to be significant, particulate taps, which are available at reasonable cost, may provide a technological solution. In any event, recovery and recycling is the preferred technique for both health and economic reasons. Details of platinum recovery and recycling from
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Polybrominated biphenyls (PBBs)
plating wastes, platinum metal refinery effluents, spent catalysts, and precious metals scrap have been published. References US Environmental Protection Agency. (April 1974). A Literature Search and Analysis of Information Regarding Uses, Production, Consumption, Reported Medical Cases and Toxicology of Platinum and Palladium, Report PB238,546. Research Triangle Park, NC National Academy of Sciences. (1977). Medical and Biologic Effects and Environmental Pollutants: Platinum Group Metals. Washington, DC Sax, N. I. (Ed.). (1981). Dangerous Properties of Industrial Materials Report, 1, No. 3, 7475 US Environmental Protection Agency. (October 31, 1985). Chemical Hazard Information Profile: Platinous Chloride. Washington, DC: Chemical Emergency Preparedness Program US Environmental Protection Agency. (October 31, 1985). Chemical Hazard Information Profile: Platinum Tetrachloride. Washington, DC: Chemical Emergency Preparedness Program New Jersey Department of Health and Senior Services. (September 2002). Hazardous Substances Fact Sheet: Platinum. Trenton, NJ
Polybrominated biphenyls (PBBs) P:0810 Molecular Formula: C12H4Br6 Common Formula: Br3C6H2C6H2Br3 Synonyms: Decabromobiphenyl; Firemaster BP-6®; Firemaster FF-1®; HBB; NCI-C53634; 2,4,5,20 ,40 ,50 Hexabromobiphenyl; PBBs; PBB (BP-6); PBB (FF-1); Polybrominated biphenyl (BP-6); Polybrominated biphenyl (FF-1); Tetrabromo(tetrabromophenyl)benzene CAS Registry Number: 36355-01-8 (hexabromobiphenyl); 27858-07-7 (octabromobiphenyl); 59536-65-1 [Firemaster BP-6 Polybrominated biphenyls category include the following: p-Bromodiphenyl ether 101-55-3 Decabromobiphenyl 13654-09-6 Decabromodiphenyl ether 1163-19-5 p,p0 Dibromodiphenyl ether 2050-47-7 Hexabromobiphenyl 59080-40-9 Hexabromo-1,10 -biphenyl 36355-01-8 Hexabromodiphenyl ether 36483-60-0 Nonabromodiphenyl ether 63936-56-1 Octabromobiphenyl 27858-07-7 Octabromobiphenyl 61288-13-9 Octabromodiphenyl ether 32536-52-0 Pentabromodiphenyl ether 32534-81-9 Polybrominated biphenyl 59536-65-1 Polybrominated biphenyl mixture 67774-32-7 Tetrabromodiphenyl ether 40088-47-9 Tribromodiphenyl ether 49690-94-0
RTECS® Number: DV5330000 (hexabromobiphenyl); LK5060000 (Firemaster BP-6); LK5065000 (Firemaster FF-1) UN/NA & ERG Number: UN3152 (Polyhalogenated biphenyls, solid)/171; UN3151 (Polyhalogenated biphenyls, liquid)/171 EC Number: 252-994-2 (hexabromobiphenyl); 248-696-7 (octabromobiphenyl or [tetrabromo(tetrabromophenyl)benzene]; 237-137-2 (decabromobiphenyl) Regulatory Authority and Advisory Bodies Carcinogenicity: IARC: Human Limited Evidence, animal Sufficient Evidence, possibly carcinogenic to humans, Group 2B; NTP: Reasonably anticipated to be a human carcinogen. Chemicals Subject to TSCA 12(b) Export Notification Requirements, Section 5: Any combination of the following substances resulting from a chemical reaction (as well as the individual chemicals): Tetrabromodiphenyl ether (CAS:40088-47-9); Pentabromodiphenyl ether (CAS: 32534-81-9); Hexabromodiphenyl ether (CAS: 36483-600); Heptabromodiphenyl ether (CAS: 68928-80-3); Octabromodiphenyl ether (CAS: 32536-52-0); Nonabromodiphenyl ether (CAS: 63936-56-1). For details, see the Proposed Significant New Use Rule (69 FR 70404, December 6, 2004). Banned or Severely Restricted (Canada, USA) (UN)[13] (Germany, EEC) (UN).[35] RCRA, 40CFR261, Appendix 8 Hazardous Constituents, waste number not listed. RCRA 40CFR264, Appendix 9; TSD Facilities Ground Water Monitoring List. Suggested test method(s) (PQL μg/ L): 8080 (50); 8250 (100). EPCRA Section 313 Form R de minimis concentration reporting level: 0.1%. California Proposition 65 Chemical: Cancer 1/1/88; Reproductive toxin 10/1/94. Canada, WHMIS, Ingredients Disclosure List Concentration 0.1% (67774-32-7). Rotterdam Convention Annex III [Chemicals Subject to the Prior Informed Consent Procedure (PIC)] [(13654-09-6 (deca-); 36355-01-8 (hexa-); 27858-07-7 (octa-)]. List of Stockholm Convention POPs: Annex A (Elimination) included in the same category are the following: hexabromobiphenyl (CAS 59080-40-9); hexabromobiphenyl ether (CAS 59080-40-9) and heptabromodiphenyl ether (CAS 68928-80-3); Tetrabromodiphenyl ether CAS (40088-47-9); and Pentabromodiphenyl ether (CAS 3253481-9). European/International Regulations: not listed in Annex 1. WGK (German Aquatic Hazard Class): No value assigned. Description: PBBs do not occur as natural products. Hexabromobiphenyl is the predominant isomer. These materials are heavy, highly brominated compounds. Typical is hexabromobiphenyl, Br3C6H2aC6H2Br3: Molecular weight 5 627.62; decomposes at 300 C to 400 C. It will be used as an illustrative example of such compounds. PBBs
Polybrominated biphenyls (PBBs) are produced by direct bromination of biphenyl, and it could be anticipated that very complex mixtures of compounds differing from each other both in number of bromine atoms per molecule and by positional isomerism are formed. The possibility also exists (analogous to the PCBs) that halogenated dibenzofurans (e.g., Brominated dibenzofurans) may be trace contaminants in certain PBB formulations. Hazard Identification (based on NFPA-704 M Rating System): Health 4, Flammability 1, Reactivity 0. Potential Exposure: The polybrominated biphenyls (PBBs) are inert substances and have been employed, primarily as fire retardants. For example, the PBBs were incorporated into thermoplastics at a concentration of about 15% to increase the heat stability of the plastic to which it is added. In 1973, 12 tons of PBBs, a highly toxic flame retardant, were accidentally mixed with an animal feed supplement and fed to cattle in Michigan. Contamination also resulted from traces of PBBs being discharged into the environment at the manufacturing site and at other facilities involved in handling PBBs. Approximately 250 dairy and 500 cattle farms were quarantined, tens of thousands of swine and cattle and more than one million chickens were destroyed, and lawsuits involving hundreds of millions of dollars were instituted. Before the nature of the contamination was recognized, many of the contaminated animals had been slaughtered, marketed, eaten; and eggs and milk of the contaminated animals were also consumed. Thus, large numbers of people have been exposed to PBBs; they are persistent in the environment and are concentrated in body fat. While commercial manufacture and distribution of PBBs have currently ceased, the full extent of the problem has not yet been assessed. Permissible Exposure Limits in Air No standards or TEEL available. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms The accidental contamination, in 1973, of animal feed and livestock throughout Michigan by polybrominated biphenyl flame retardants (Firemaster BP-6) has stimulated extensive studies of the potential for water contamination, transport, bioaccumulation, biological and toxicological nature of this class of environmental agent. While no immediate adverse health effects were noted in several thousand Michigan farm families that consumed milk and dairy products contaminated with PBBs, it is not possible to determine at this date any chronic or delayed effects that might be attributed to the PBBs or the potential ability of this chemical to cause birth defects. Firemaster FF-1 (Firemaster BP-6 containing 2% of calcium trisilicate)—a mixture of pentabromobiphenyl, hexabromobiphenyl, and heptabromobiphenyl, with hexabromobiphenyl being the major component—administered by gavage produced neoplastic nodules and hepatocellular carcinomas in female Sherman strain rats. In another bioassay, Firemaster FF-1, also administered by gavage, was carcinogenic to Fisher 344 rats and B6C3F1 mice of each sex,
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inducing neoplastic nodules, hepatocellular carcinomas, and chloangiocarcinomas in rats and hepatocellular carcinomas in mice. Long Term Exposure: Confirmed carcinogen. Experimental teratogenic and reproductive effects. Mutation data reported. Points of Attack: Liver, kidneys, skin. Medical Surveillance: Consider the points of attack in preplacement and periodic physical examinations. Liver and kidney function tests. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. A regulated, marked area should be established where this chemical is handled, used, or stored in compliance with OSHA Standard 1910.1045. Shipping: Polyhalogenated biphenyls, liquid, require a shipping label of “CLASS 9.” They fall in Hazard Class 9 and Packing Group II. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is
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Polychlorinated biphenyls (PCBs)
complete. Remove all ignition sources. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: Poisonous gases are produced in fire, including bromine. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. References US Environmental Protection Agency. (December 1979). Status Assessment of Toxic Chemicals: Polybrominated Biphenyls, Report EPA-600/2-79-210k. Washington, DC National Toxicology Program. (1982). NTP: Technical Report on the Toxicology and Carcinogenesis Bioassay of Polybrominated Biphenyl Mixture (Firemaster FF-1), Technical Report Series No. 244, NIH Publication No. 821800. Research Triangle Park, NC
Polychlorinated biphenyls (PCBs) P:0820 Molecular Formula: C12H102XClX Synonyms: Aroclor; Aroclor 1221; Aroclor 1232; Aroclor 1242; Aroclor 1248; Aroclor 1254; Aroclor 1260; Aroclor 1262; Aroclor 1268; Aroclor 2565; Aroclor 4465; Biphenyl, Chlorinated; 1,10 -Biphenyl, chloro derivs.; Biphenyl, polychloro-; Chlophen; Chlorextol; Chlorinated biphenyl; Chlorinated diphenyl; Chlorinated diphenylene; Chloro biphenyl; Chloro 1,1-biphenyl; Clophen; Dykanol; Diphenyl, chlorinated; Fenclor; Inerteen; Kanechlor; Kanechlor 300; Kanechlor 400; Kanechlor 500; Montar; Noflamol; PCB; PCBS; Phenochlor; Phenoclor; Polychlorobiphenyl; Pyralene; Pyranol; Santotherm; Santotherm FR; Sovol; the rminol FR-1 CAS Registry Number: 1336-36-3 (Aroclor PCBs); 5346921-9; (alt.) 11104-29-3 (Aroclor 1242) (42% Cl); 12672-296 (Aroclor 1248) (48% Cl); 11097-69-1 (Aroclor 1254) (54% Cl); 11096-82-5 (Aroclor 1260) (60% Cl); 37324-235 (Aroclor 1262) (62% Cl); 11100-14-4 (Aroclor 1268) (68% Cl); 55720-99-5 (PCB oxide)
RTECS® Number: TQ1350000; TQ1356000 (Aroclor 1242) (42% Cl); TQ1358000 (Aroclor 1248) (48% Cl); TQ1360000 (Aroclor 1254) (54% Cl); TQ1362000 (Aroclor 1260) (60% Cl); TQ1364000 (Aroclor 1262) (62% Cl); TQ1366000 (Aroclor 1268) (68% Cl) UN/NA & ERG Number: UN2315/171 EC Number: 215-648-1 [Annex I Index No.: 602-039-00-4] (PCBs) Regulatory Authority and Advisory Bodies Carcinogenicity: (1336-36-3): Carcinogenicity: IARC: Animal Sufficient Evidence; Human Limited Evidence, Group 2A, 1998; EPA: Sufficient evidence from animal studies; inadequate evidence or no useful data from epidemiologic studies; NTP: Reasonably anticipated to be a human carcinogen; NIOSH: Potential occupational carcinogen. Chemicals Subject to TSCA 12(b) Export Notification Requirements, Section 6. Rotterdam Convention Annex III [Chemicals Subject to the Prior Informed Consent Procedure (PIC)] as PCBs. Aroclor 1242 NTP: 11th Report on Carcinogens, 2002: Reasonably anticipated to be a human carcinogen; IARC (PCB): Animal Sufficient Evidence; Human Limited Evidence, Group 2A, 1987; EPA (PCB): Sufficient evidence from animal studies; inadequate evidence or no useful data from epidemiologic studies. Aroclor 1254 NTP: 11th Report on Carcinogens, 2004: Reasonably anticipated to be a human carcinogen; NCI: Carcinogenesis Bioassay (feed); equivocal evidence: rat; IARC (PCB): Animal Sufficient Evidence; Human Limited Evidence, Group 2A, 1987; EPA (PCB): Sufficient evidence from animal studies; inadequate evidence or no useful data from epidemiologic studies. US EPA Gene-Tox Program, Negative: Cytogenetics—male germ cell; Rodent dominant lethal (Aroclor 1242); Negative: SHE—clonal assay; Rodent dominant lethal; Negative: Sperm morphology—mouse; Inconclusive: Mammalian micronucleus (Aroclor 1254). Banned or Severely Restricted (many countries) (UN).[13] Persistent Organic Pollutants (UN). Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Clean Air Act: Hazardous Air Pollutants (Title I, Part A, Section 112). Clean Water Act: Section 311 Hazardous Substances/RQ 40CFR117.3 (same as CERCLA, see below); 40CFR401.15 Section 307 Toxic Pollutants; 40CFR423, Appendix A. Priority Pollutants; Section 313 Water Priority Chemicals (57FR41331, 9/9/92). RCRA 40CFR268.48; 61FR15654, Universal Treatment Standards: Wastewater (mg/L), 0.10; Nonwastewater (mg/ kg), 10, total PCBs, sum of all PCB isomers, or all AROCLORS. RCRA 40CFR264, Appendix 9; TSD Facilities Ground Water Monitoring List. Suggested test method(s) (PQL μg/L): 8080 (50); 8250 (100).
Polychlorinated biphenyls (PCBs) Safe Drinking Water Act: MCL, 0.0005 mg/L; MCLG, zero; Regulated chemical (47 FR 9352). Reportable Quantity (RQ): 1 lb (0.454 kg). EPCRA Section 313 Form R de minimis concentration reporting level: 0.1%. US DOT Regulated Marine Pollutant (49CFR172.101, Appendix B), severe pollutant. California Proposition 65 Chemical: Cancer 10/1/89; Reproductive toxin 1/1/91; (containing $ 60% chlorine by molecular weight) 1/1/88. Canada, WHMIS, Ingredients Disclosure List Concentration 0.1%. Note: The EPA requires the following: All PCB transformer locations must be cleared of stored combustible materials (solvents, paints, paper, etc.). All PCB transformers must be registered with the local fire department. All PCB-containing equipment must be posted with a large yellow label and the exterior door of the vault, machinery room door and any other means of exit must also be marked with PCB yellow ID labels. All PCB-containing transformers must be inspected every 3[3] weeks; leaks must be repaired within 2[2] days and reported to the EPA within 5[5] days. In order to prevent fires, EPA recently required that high-voltage network transformers be removed and that enhanced electrical protection be added on many types of PCB transformers in commercial buildings. List of Stockholm Convention POPs: Annex A (Elimination); Annex C (Unintentional production and release) as PCBs. European/International Regulations: Hazard Symbol (PCB): Xn, N; Risk phrases: R33; R50/53; Safety phrases: S2; S35; S60; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): 3—Severe hazard to waters. Description: Arochlor 1242 is a colorless to light yellow-colored viscous liquid with a mild, hydrocarbon odor. Molecular weight 5 258 (approx.); Specific gravity (H2O:1) 5 1.39 at 25 C; Boiling point 5 325366 C; Freezing/Melting point 5 18 C; Vapor pressure 5 0.001 mmHg at 25 C. Insoluble in water. Arochlor 1254 is a colorless to pale-yellow, viscous liquid (resinous state) or solid (below 10 C) with a mild, hydrocarbon odor. Molecular weight 5 326 (approx.); Specific gravity (H2O:1) 5 1.39 at 25 C; Boiling point 5 365390 C; Freezing/Melting point 5 18 C; Vapor pressure 5 0.00006 mmHg at 25 C. Insoluble in water. Hazard Identification (based on NFPA-704 M Rating System): Health 2, Flammability 1, Reactivity 0. C12H10 2 xClx, diphenyl rings, in which one or more hydrogen atoms are replaced by a chlorine atom. Most widely used are chlorodiphenyl (42% chlorine), containing 3 chlorine atoms in unassigned positions, and chlorodiphenyl (54% chlorine) containing 5 chlorine atoms in unassigned positions. These compounds are light, straw-colored liquids with typical chlorinated aromatic odors; 42% chlorodiphenyl is a mobile liquid and 54% chlorodiphenyl is a viscous liquid. Insoluble in water. Polychlorinated biphenyls are prepared by the
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chlorination of biphenyl and hence are complex mixtures containing isomers of chlorobiphenyls with different chlorine contents. It should be noted that there are 209 possible compounds obtainable by substituting chlorine for hydrogen from 110 different positions on the biphenyl ring system. An estimated 4070 different chlorinated biphenyl compounds can be present in each of the higher chlorinated commercial mixtures. For example, Aroclor 1254 contains 69 different molecules, which differ in the number and position of chlorine atoms. It should also be noted that certain PCB commercial mixtures (no longer produced in the United States) but produced in France, Germany, and Japan have been shown to contain other classes of chlorinated derivatives, e.g., chlorinated naphthalenes and chlorinated dibenzofurans. The possibility that naphthalene and dibenzofuran contaminate the technical biphenyl feedstock used in the preparation of the commercial PCB mixtures cannot be excluded. Potential Exposure: Compound Description (Aroclor 1242): Agricultural Chemical; Tumorigen, Mutagen; Reproductive Effector; Human Data; (Aroclor 1254) Agricultural Chemical; Tumorigen, Mutagen; Reproductive Effector. PCBs are mixtures of individual chemicals which are no longer produced in the United States but are still found in the environment. Chlorinated diphenyls are used alone and in combination with chlorinated naphthalenes. They are stable, thermoplastic, and nonflammable; they are used in heat transfer and hydraulic fluids, lubricants, and insecticide formulations; they found use in insulation for electric cables and wires; in the production of electric condensers; as additives for extreme pressure lubricants; and as a coating in foundry use. Polychlorinated biphenyls (PCBs, first introduced into commercial use more than 45 years ago) are one member of a class of chlorinated aromatic organic compounds which are of increasing concern because of their apparent ubiquitous dispersal, persistence in the environment, and tendency to accumulate in food chains, with possible adverse effects on animals at the top of food webs, including man. Incompatibilities: Strong oxidizers. Permissible Exposure Limits in Air Protective Action Criteria (PAC) 1336-36-3 (Aroclor PCBs); (42% Cl) TEEL-0: 0.04 mg/m3 PAC-1: 0.125 mg/m3 PAC-2: 0.75 mg/m3 PAC-3: 500 mg/m3 12674-11-2 (Aroclor 1016) TEEL-0: 12.5 mg/m3 PAC-1: 40 mg/m3 PAC-2: 300 mg/m3 PAC-3: 500 mg/m3 53469-21-9; (Aroclor 1242) (42% Cl) TEEL-0: 1 mg/m3 PAC-1: 1 mg/m3 PAC-2: 1 mg/m3
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Polychlorinated biphenyls (PCBs)
PAC-3: 500 mg/m3 11104-28-2 (Aroclor 1221) (21% Cl); 11141-16-5 (Aroclor 1232) (32% Cl); 12672-29-6 (Aroclor 1248) (48% Cl) TEEL-0: 3 mg/m3 PAC-1: 7.5 mg/m3 PAC-2: 60 mg/m3 PAC-3: 500 mg/m3 11097-69-1 (Aroclor 1254) (54% Cl) TEEL-0: 0.5 mg/m3 PAC-1: 35 mg/m3 PAC-2: 250 mg/m3 PAC-3: 400 mg/m3 11096-82-5 (Aroclor 1260) (60% Cl); (Aroclor 1261/1262) (61% Cl) TEEL-0: 0.4 mg/m3 PAC-1: 1.25 mg/m3 PAC-2: 7.5 mg/m3 PAC-3: 500 mg/m3 37324-23-5 (Aroclor 1262) (62% Cl) TEEL-0: 0.6 mg/m3 PAC-1: 1.5 mg/m3 PAC-2: 12.5 mg/m3 PAC-3: 500 mg/m3 11100-14-4 (Aroclor 1268) (68% Cl) TEEL-0: 0.0125 mg/m3 PAC-1: 0.04 mg/m3 PAC-2: 0.3 mg/m3 PAC-3: 500 mg/m3 OSHA PEL: 1 mg/m3 TWA [skin] NIOSH REL: 0.001 mg/m3 TWA (The REL also applies to other PCBs); A potential occupational carcinogen. Limit exposure to lowest feasible concentration. See NIOSH Pocket Guide, Appendix A. ACGIH TLV®[1]: 1 mg/m3 TWA [skin]. DFG MAK: 0.1 ppm/1.1 mg/m3 TWA; Peak Limitation Category II(8) [skin]; Carcinogen Category 3B; Pregnancy Risk Group B. NIOSH IDLH: potential occupational carcinogen 5 mg/m3. Australia: TWA 1 mg/m3; STEL 2 mg/m3, [skin], carcinogen, 1993; Austria: MAK 0.1 ppm (1 mg/m3), [skin], suspected carcinogen, 1999; Belgium: TWA 1 mg/m3; STEL 2 mg/m3, [skin], 1993; Finland: TWA 0.5 mg/m3; STEL 1.5 mg/m3, [skin], 1993; France: VME 1 mg/m3, [skin], 1999; Japan: 0.1 mg/m3, [skin], 2A carcinogen, 1999; the Netherlands: MAC-TGG 1 mg/m3, [skin], 2003; the Philippines: TWA 1 mg/m3, [skin], 1993; Poland: MAC (TWA) 1 mg/m3, 1999; Sweden: NGV 0.01 mg/m3, KTV 0.3 mg/m3, [skin], carcinogen, 1999; Switzerland: MAK-W 0.1 ppm (1 mg/m3), [skin], 1999; United Kingdom: TWA 0.1 mg/m3, [skin], 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: TWA 1 mg/m3 [skin] 54% chlorine OSHA PEL: 0.5 mg/m3 TWA [skin]. NIOSH REL: 0.001 mg/m3 (applies to all PCBs) TWA [skin]. See NIOSH Pocket Guide, Appendix A.
ACGIH TLV®[1]: 0.5 mg/m3 TWA [skin]; confirmed animal carcinogen with unknown relevance to humans. DFG MAK: 0.05 ppm/0.70 mg/m3 TWA; Peak Limitation Category II(8) [skin]; Carcinogen Category 3B; Pregnancy Risk Group B. NIOSH IDLH: 5 mg/m3. Australia: TWA 0.5 mg/m3; STEL 1 mg/m3, [skin], Carcinogen, 1993; Austria: MAK 0.05 ppm (0.5 mg/m3), [skin], suspected carcinogen, 1999; Belgium: TWA 0.5 mg/ m3; STEL 1 mg/m3, [skin], 1993; France: VME 0.5 mg/m3, [skin], 1999; Japan: 0.1 mg/m3, [skin], 2A carcinogen, 1999; Norway: TWA 0.01 mg/m3, 1999; the Netherlands: MAC-TGG 0.5 mg/m3, [skin], 2003; Poland: MAC (TWA) 1 mg/m3, 1999; Sweden: NGV 0.1 mg/m3, KTV 0.3 mg/m3, [skin], carcinogen, 1999; Switzerland: MAK-W 0.05 ppm (0.5 mg/m3), [skin], 1999; Turkey: TWA 1 mg/m3, [skin], 1993; United Kingdom: TWA 0.1 mg/m3, [skin], 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: confirmed animal carcinogen with unknown relevance to humans. The Czech Republic has set a TWA of 0.5 mg/m3 and a ceiling value of 1.0 mg/m3. PCB oxide 0.5 mg/m3, inhalable fraction [skin]. Several states have set guidelines or standards for PCB’s in ambient air[60] as follows (all in μg/m3). Determination in Air: Use NIOSH Analytical Method #5503, Polychlorobiphenyls; #8004, Polychlorobiphenyls in serum; #PV-2089, Chlorodiphenyl (42% Chlorine); #PV2088, Chlorodiphenyl (54% Chlorine). Permissible Concentration in Water: To protect freshwater aquatic life: 0.014 μg/L as a 24-h average. To protect saltwater aquatic life: 0.030 μg/L as a 24-h average. To protect human health: preferably zero. An additional lifetime cancer risk of 1 in 100,000 results at a level of 0.00079 μg/L.[6] The EPA has set a maximum contaminant level of 0.0005 milligrams PCBs per liter of drinking water (0.0005 mg/L). The EPA requires that spills of 1 lb or more of PBCs be reported to the EPA. Determination in Water: Gas chromatography (EPA Method 608) or gas chromatography plus mass spectrometry (EPA Method 625). Octanolwater coefficient: Log Kow 5 6.25 (54% Chlorine) (estimated). Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Inhalation of fume or vapor and percutaneous absorption of liquid, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Inhalation: May produce irritation to nose, throat, and lungs. The vapors can cause coughing and/or difficulty in breathing. Levels above 10 mg/m3 are reported to be unbearable. Inhalation may contribute significantly to all symptoms of long-term exposure. Skin: Absorption moderate. Contributes significantly to all symptoms of long-term exposure. Sensitized individuals may develop a rash after 2 days exposure by contact or inhalation. Eyes: May produce irritation and burns. Levels of
Polychlorinated biphenyls (PCBs) 10 mg/m3 are severely irritating. Ingestion: Absorption in digestive system contributes significantly to all symptoms of long-term exposure. There are no reported deaths of humans due to a single ingestion. However, experiments in animals suggest that ingestion of 610 fluid ounces would cause death to a healthy a 150-lb adult. Long Term Exposure: Repeated or prolonged contact with skin may cause acne-like skin rash (chloroacne). The substance may cause liver damage. High exposure can damage the nervous system. PCBs are readily absorbed into the body by all routes of exposure. They may persist in tissues for years after exposure stops. The symptoms below may be due to PCBs or to chemical contaminants. High levels of PCB vapor, 110 mg/m3, may produce burning feeling in eyes, nose, and face; dry throat; lung and throat irritation; nausea, dizziness, and aggravation of acne. These may be felt immediately or be delayed weeks or months. Chemical acne, black heads, dark patches on skin, and unusual eye discharge have been reported by all routes of exposure. Although some sensitive individuals have reported these effects after 2 days, onset may not occur for months. These effects may last for months. Digestive disturbance have been reported in some individuals. PCBs may impair the function of the immune system. High levels of PCBs have been shown to produce cancer and birth defects in laboratory animals. Whether PCBs produce these effects in humans is not known. Points of Attack: Liver, skin, nervous system. Cancer site in animals: liver. Medical Surveillance: NIOSH lists the following tests: Adipose Tissue; whole blood (chemical/metabolite); blood serum; blood plasma; liver function tests. Before beginning employment and at regular times after that, the following are recommended: Serum Triglycerides level. Examination of the skin. Examination of the nervous system. Nerve conduction studies should be considered. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Chlorodiphenyl (42% chlorine) 53469-21-9. Prevent skin contact. 8 h (more than 8 h of resistance to breakthrough .0.1 μg/cm/min): butyl rubber gloves, suits, boots; Neoprene™ rubber gloves, suits, boots; Teflon™ gloves, suits, boots; Viton™ gloves, suits; Saranex™ coated suits,
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Barricade™ coated suits; Responder™ suits; 4 h (At least 4 but ,8 h of resistance to breakthrough .0.1 μg/cm2/min): 4H™ and Silver Shield™ gloves. Chlorodiphenyl (54% chlorine) 11097-69-1. Prevent skin contact. 8 h (more than 8 h of resistance to breakthrough .0.1 μg/cm/min): butyl rubber gloves, suits, boots; Neoprene™ rubber gloves, suits, boots; Teflon™ gloves, suits, boots; Viton™ gloves, suits, Saranex™ coated suits, Barricade™ coated suits; Responder™ suits; 4 h (At least 4 but ,8 h of resistance to breakthrough .0.1 μg/cm2/min): 4H™ and Silver Shield™ gloves. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Specific engineering controls are recommended in NIOSH Criteria Document: #77-225, Occupational Exposure to Polychlorinated Biphenyls. Respirator Selection: NIOSH: At any detectable concentration: SCBAF: Pd,Pp (APF 5 10,000) (any self-contained breathing apparatus that has a full facepiece and is operated in a pressure-demand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary, self-contained breathing apparatus operated in a pressuredemand or other positive-pressure mode). Escape: GmFOv100 (APF 5 50) (any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or backmounted organic vapor canister having an N100, R100, or P100 filter) or SCBAE (any appropriate escape-type, selfcontained breathing apparatus). Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with these chemicals you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, wellventilated area away from strong oxidizers (such as chlorine, bromine, and fluorine). A regulated, marked area should be established where this chemical is handled, used, or stored in compliance with OSHA Standard 1910.1045. Shipping: Polychlorinated biphenyls require a shipping label of “CLASS 9.” They fall in DOT Hazard Class 9 and Packing Group II. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Ventilate area of spill or leak. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless
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Portland cement
the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Spills of 1[1] lb or more must be reported to the EPA. Fire Extinguishing: PCBs may burn but do not easily ignite. Poisonous gases, including dioxin and chlorinated dibenzofurans, are produced in fire. Use dry chemical, carbon dioxide, or alcohol foam extinguishers. Vapors are heavier than air and will collect in low areas. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Incineration at 1648 C with scrubbing to remove any chlorine-containing products. In addition, some chemical waste landfills have been approved for PCB disposal. More recently, treatment with metallic sodium has been advocated which yields a low molecular weight polyphenylene and sodium chloride. References National Institute for Occupational Safety and Health. (1977). Criteria for a Recommended Standard: Occupational Exposure to Polychlorinated Biphenyls, NIOSH Document No. 77-225 US Environmental Protection Agency. (1980). Polychlorinated Biphenyls: Ambient Water Quality Criteria. Washington, DC National Academy of Sciences. (1979). Polychlorinated Biphenyls. Washington, DC World Health Organization. (1976). Polychlorinated Biphenyls and Triphenyls, Environmental Health Criteria No. 2. Geneva, Switzerland Sax, N. I. (Ed.). Dangerous Properties of Industrial Materials Report, 3, No. 4, 95100 (1983) and 6, No. 2, 2834 (1986) US Public Health Service. (November 1987). Toxicological Profile for Selected PCB’s. Atlanta, GA: Agency for Toxic Substances and Disease Registry
New York State Department of Health. (March 1986). Chemical Fact Sheet: PCB’s. Version 2. Albany, NY: Bureau of Toxic Substance Assessment New Jersey Department of Health and Senior Services. (April 2002). Hazardous Substances Fact Sheet: Polychlorinated Biphenyls. Trenton, NJ
Portland cement
P:0830
Molecular Formula: Ca2O4Si; Al2Ca3O6; Ca3O5Si; Al2Ca4Fe2O10 Common Formula: 2CaO SiO2; 3CaO Al2O3; 3CaO SiO2; 4CaO Al2O3 Fe2O3 Synonyms: Cement; Hydraulic cement; Portland cement silicate CAS Registry Number: 65997-15-1; 68475-76-3 (flue dust, portland cement) RTECS® Number: VV8770000 EC Number: 266-043-4; 270-659-9 (flue dust, portland cement) Regulatory Authority and Advisory Bodies Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Description: Portland cement is a class of hydraulic cements containing tri- and dicalcium silicate in addition to varying amounts of alumina, tricalcium aluminate, and iron oxide. The quartz content of most is below 1%. The average composition of regular Portland cement is as follows: CaO (64.0%); SiO2 (21.0%); Al2O3 (5.8%); Fe2O3 (2.9%); MgO (2.5%); Alkali oxides (1.4%); SO3 (1.7%). Freezing/ Melting point 5 .1050 C. Reacts with water. Potential Exposure: Cement is used as a binding agent in mortar and concrete (a mixture of cement, gravel, and sand). Potentially hazardous exposure may occur during both the manufacture and use of cement. Incompatibilities: None reported. Permissible Exposure Limits in Air OSHA PEL: 50 mppcf TWA or 15 mg/m3, total dust TWA; 5 mg/m3 TWA, respirable fraction. NIOSH REL: 10 mg/m3, total dust TWA; 5 mg/m3 TWA, respirable fraction. ACGIH TLV®[1]: 1 mg/m3, respirable fraction TWA the value is for particulate matter containing no asbestos and ,1% crystalline silica (free SiO2), not classifiable as a human carcinogen. NIOSH IDLH: 5000 mg/m3. No TEEL available. Australia: TWA 10 mg/m3, 1993; Belgium: TWA 10 mg/m3, 1993; Sweden: NGV 10 mg/m3 (total dust), 1999; Sweden: NGV 5 mg/m3 (respirable dust), 1999; Switzerland: MAK-W 6 mg/m3, 1999; United Kingdom: TWA 10 mg/m3, total inhalable dust, 2000; the Netherlands: MAC-TGG 10 mg/m3, 2003; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: TWA 10 mg/m3 for
Portland cement particulate matter containing no asbestos and ,1% crystalline silica (free SiO2). Determination in Air: NIOSH Analytical Method (IV) #0500, Particulates NOR, total dust; OSHA Analytical Method ID-207, Portland cement (total dust). Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Irritates the eyes, skin, and nose with cough, expectoration, exertional dyspnea (breathing difficulty), wheezing. Long Term Exposure: May cause chronic bronchitis. Exposure may produce cement dermatitis which is usually due to primary irritation from the alkaline, hygroscopic, and abrasive properties of cement. Chronic irritation of the eyes and nose may occur. In some cases, cement workers have developed an allergic sensitivity to constituents of cement, such as hexavalent chromate. It is not unusual for cement dermatitis to be prolonged and to involve covered areas of the body. No documented cases of pneumoconiosis or other systemic manifestations attributed to finished Portland cement exposure have been reported. Conflicting reports of pneumoconiosis from cement dust appear related to exposures that occurred in mining, quarrying, or crushing silicacontaining raw materials. Points of Attack: Respiratory system, eyes, skin. Medical Surveillance: NIOSH lists the following tests: chest X-ray; pulmonary function tests: forced vital capacity, forced expiratory volume (1 s). Preemployment and periodic medical examinations should stress significant respiratory problems, smoking history, and allergic skin sensitivities. The eyes should be examined. Patch test studies may be useful in dermatitis cases. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent prolonged skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap
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when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: NIOSH: Up to 50 mg/m3: Qm (APF 5 25) (any quarter-mask respirator). Up to 100 mg/m3: 95XQ (APF 5 10) (any particulate respirator equipped with an N95, R95, or P95 filter (including N95, R95, and P95 filtering face-pieces) except quarter-mask respirators. The following filters may also be used: N99, R99, P99, N100, R100, P100) or Sa (APF 5 10) (any supplied-air respirator). Up to 250 mg/m3: Sa:Cf (APF 5 25) (any supplied-air respirator operated in a continuous-flow mode) or PaprHie (APF 5 25) (any powered, air-purifying respirator with a high-efficiency particulate filter). Up to 500 mg/m3: 100F (APF 5 50) (any air-purifying, full-facepiece respirator with an N100, R100, or P100 filter) or SaT: Cf (APF 5 50) (any supplied-air respirator that has a tightfitting face-piece and is operated in a continuous-flow mode) or PaprTHie (APF 5 50) (any powered, air-purifying respirator with a tight-fitting face-piece and a high-efficiency particulate filter) or SCBAF (APF 5 50) (any selfcontained breathing apparatus with a full face-piece) or SaF (APF 5 50) (any supplied-air respirator with a full facepiece). Up to 5000 mg/m3: Sa: Pd,Pp (APF 5 1000) (any supplied-air respirator operated in a pressure-demand or other positive-pressure mode). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd,Pp (APF 5 10,000) (any NIOSH/MSHA- or European Standard EN 149-approved self-contained breathing apparatus that has a full face-piece and is operated in a pressuredemand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary, self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: 100F (APF 5 50) (any air-purifying, full-face-piece respirator with an N100, R100, or P100 filter) or SCBAE (any appropriate escape-type, self-contained breathing apparatus). Storage: Color Code—Green: General storage may be used. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, well-ventilated area. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable.
2200
Potassium metal
Fire Extinguishing: This chemical is a noncombustible solid. Use any extinguishers suitable for surrounding fire. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Landfill. In some cases, recovery of cement from cement kiln dust or ready-mix concrete residues may be economic, and the technology is available.
Potassium metal
P:0840
Molecular Formula: K Synonyms: Elemental potassium; Kalium CAS Registry Number: 7440-09-7 RTECS® Number: TS6460000 UN/NA & ERG Number: UN2257/130; UN1420 (metal alloys)/138; metal powder, in bulk, may be pyrophoric: UN3089 (Metal powder, flammable, n.o.s.)/170 EC Number: 231-119-8 [Annex I Index No.: 019-001-00-2] Regulatory Authority and Advisory Bodies European/International Regulations: Hazard Symbol: F, C; Risk phrases: R14; R34; Safety phrases: S1/2; S5 (If appropriate); S8; S45 (see Appendix 4). WGK (German Aquatic Hazard Class): No value assigned. Description: Potassium is a soft silvery metal. Molecular weight 5 39.10; Boiling point 5 774 C; Freezing/Melting point 5 64 C; Autoignition temperature 5 441 C. Hazard Identification (based on NFPA-704 M Rating System) (lump): Health 3, Flammability 3, Reactivity 3 . Reacts violently with water. Potential Exposure: Used as a reagent and in sodium potassium alloys which are used as high-temperature heat transfer media. Incompatibilities: Air contact causes spontaneous ignition. Violent reaction with water, forming heat, spattering, corrosive potassium hydroxide, and explosive hydrogen. The heat from the reaction can ignite the hydrogen that is generated. A powerful reducing agent. Violent reaction with oxidizers, organic materials, carbon dioxide, heavy metal compounds, carbon tetrachloride, halogenated hydrocarbons, easily oxidized materials, and many other substances. Store under nitrogen, mineral oil, or kerosene. Oxidizes and forms unstable peroxides under storage conditions. Potassium metal containing an oxide coating is an extremely dangerous explosion hazard and should be removed and destroyed. Permissible Exposure Limits in Air Protective Action Criteria (PAC) TEEL-0: 0.075 mg/m3 PAC-1: 0.2 mg/m3 PAC-2: 1.5 mg/m3 PAC-3: 300 mg/m3
Permissible Concentration in Water: No criteria set. (Reacts with water). Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Potassium can affect you when breathed in. Inhalation of dusts or mists can irritate the eyes, nose, throat, and lungs with sneezing, coughing, and sore throat. Higher exposures may cause a buildup of fluid in the lungs (pulmonary edema). This can cause death. Skin and eye contact can cause severe burns leading to permanent damage. Long Term Exposure: Prolonged exposure to fumes can cause sores of the inner nose and nasal septum. Fumes can irritate the lungs; bronchitis may develop. Points of Attack: Lungs, skin Medical Surveillance: Before beginning employment and at regular times after that, for those with frequent or potentially high exposures, the following are recommended: lung function tests. If symptoms develop or overexposure is suspected, the following may be useful: consider chest X-ray after acute overexposure. First Aid: Eye Contact: Immediately remove any contact lenses and flush with large amounts of water. Continue without stopping for at least 30 min, occasionally lifting upper and lower lids. Seek medical attention immediately. Skin Contact: Quickly remove contaminated clothing. Immediately wash area with large amounts of water. Seek medical attention immediately. Breathing: Remove the person from exposure. Begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Where there is potential for exposure to potassium, use a NIOSH/MSHA- or European Standard EN149-approved respirator equipped with particulate (dust/ fume/mist) filters. Particulate filters must be checked every day before work for physical damage, such as rips or tears, and replaced as needed. Where there is potential for high exposures, use a NIOSH/MSHA- or European Standard EN149-approved supplied-air respirator with a full
Potassium arsenate face-piece operated in the positive mode or with a full facepiece, hood, or helmet in the continuous-flow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—Red Stripe (lump): Flammability Hazard: Do not store in the same area as other flammable materials. Prior to working with this chemical you should be trained on its proper handling and storage. Potassium must be stored to avoid contact with carbon monoxide and moisture, compounds of heavy metals (such as silver oxide and silver chloride) and carbon tetrachloride since violent reactions occur. Store under nitrogen, mineral oil, or kerosene. Sources of ignition, such as smoking and open flames, are prohibited where potassium metal is used, handled, or stored in a manner that could create a potential fire or explosion hazard. Shipping: Potassium requires a shipping label of “DANGEROUS WHEN WET.” It falls in Hazard Class 4.3 and Packing Group II. Potassium, metal alloys, requires a shipping label of “DANGEROUS WHEN WET.” It falls in Hazard Class 4.3 and Packing Group II. For Metal powder, flammable, n.o.s. the required label is “SPONTANEOUSLY COMBUSTIBLE.” They fall in Hazard Class 4.2 and Packing Group II. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. Keep potassium out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: Potassium is spontaneously combustible. Use dry chemical, dry graphite, soda ash, or lime extinguishers. Do not use water, carbon dioxide, or foam. Potassium may ignite in the presence of moisture or itself if exposed to air. Poisonous gases are produced in fire. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be
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trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positivepressure mode. Reference New Jersey Department of Health and Senior Services. (May 2003). Hazardous Substances Fact Sheet: Potassium. Trenton, NJ
Potassium arsenate
P:0850
Molecular Formula: AsH2KO4 Common Formula: KH2AsO4 Synonyms: Arsenic acid, Monopotassium salt; Arseniato potasico (Spanish); Macquer’s salt; Monopotassium arsenate; Monopotassium dihydrogen arsenate; Potassium acid arsenate; Potassium arsenate, monobasic; Potassium dihydrogen arsenate; Potassium hydrogen arsenate CAS Registry Number: 7784-41-0 RTECS® Number: CG1100000 UN/NA & ERG Number: UN1677/151 EC Number: 232-065-8 Regulatory Authority and Advisory Bodies Carcinogenicity: NTP: 11th Report on Carcinogens, 2004: Known to be a human carcinogen; IARC: Human Sufficient Evidence, 1980; Animal Limited Evidence, carcinogenic to humans, Group 1, 1987. Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Clean Water Act: Section 311 Hazardous Substances/RQ 40CFR117.3 (same as CERCLA, see below); Section 313 Water Priority Chemicals (57FR41331, 9/9/92). Reportable Quantity (RQ): 1 lb (0.454 kg). California Proposition 65 Chemical: Cancer 2/27/87. Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. As arsenic compounds: Clean Air Act: Hazardous Air Pollutants (Title I, Part A, Section 112) as arsenic compounds. Clean Water Act: Toxic Pollutant (Section 401.15) as arsenic and compounds. RCRA, 40CFR261, Appendix 8 Hazardous Constituents, waste number not listed. Reportable Quantity (RQ): 1 lb (0.454 kg). EPCRA (Section 313): Includes any unique chemical substance that contains arsenic as part of that chemical’s infrastructure. Form R de minimis concentration reporting level: inorganics 0.1%; organics 1.0%. US DOT Regulated Marine Pollutant (49CFR172.101, Appendix B) as arsenates, liquid, n.o.s.; arsenates, solid, n.o.s.; arsenical pesticides liquid, toxic, flammable, n.o.s. California Proposition 65 Chemical: (inorganic arsenic) Cancer 2/27/87.
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Potassium arsenate
Canada: Priority Substance List & Restricted Substances/ Ocean Dumping FORBIDDEN (CEPA), National Pollutant Release Inventory (NPRI) (arsenic compounds). European/International Regulations: Hazard Symbol: T, N; Risk phrases: R45; R23/25; R50/53; Safety phrases: S53; S45; S60; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): 3—Severe hazard to waters. Description: Potassium arsenate is a colorless to white crystalline solid. Molecular weight 5 180.04; Specific gravity 5 3.74; Boiling point 5 463 C; Freezing/Melting point 5 288 C. Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 0, Reactivity 1. Potential Exposure: Compound Description: Tumorigen. Potassium arsenate is used in the textile, tanning, preserving hides; in the textile printing and paper industries; and as an insecticide in fly baits, especially for fly paper; as laboratory reagent. Incompatibilities: A weak base. Reacts with strong oxidizers, bromine azide, acids and decomposes on contact with strong acids producing acetic acid fumes. Arsine, a very deadly gas, can be released in the presence of acid, acid mists, or hydrogen gas. Permissible Exposure Limits in Air OSHA PEL: 0.010 mg[As]/m3 TWA; cancer hazard that can be inhaled. See [1910.1018]. NIOSH REL: 0.002 mg[As]/m3 15 min Ceiling Concentration. A potential occupational carcinogen. Limit exposure to lowest feasible concentration; See Appendix A. ACGIH TLV®[1]: 0.01 mg[As]/m3 TWA; Confirmed Human Carcinogen. NIOSH IDLH: potential occupational carcinogen 5 mg [As]/m3. Protective Action Criteria (PAC) TEEL-0: 0.024 mg/m3 PAC-1: 0.35 mg/m3 PAC-2: 2.5 mg/m3 PAC-3: 12 mg/m3 DFG TRK: 0.10 mg[As]/m3; BAT: 1.30 μg[As]/L in urine/ end-of-shift; Carcinogen Category 1. Arab Republic of Egypt: TWA 0.2 mg/m3, 1993; Australia: TWA 0.05 mg/m3, carcinogen, 1993; Belgium: TWA 0.2 mg/m3, 1993; Denmark: TWA 0.05 mg/m3, 1999; Finland: carcinogen, 1993; France: VME 0.2 mg/m3, 1993; Hungary: STEL 0.5 mg/m3, carcinogen, 1993; India: TWA 0.2 mg/m3, 1993; Norway: TWA 0.02 mg/m3, 1999; the Philippines: TWA 0.5 mg/m3, 1993; Poland: MAC (TWA) 0.01 mg/m3, 1999; Sweden: NGV 0.03 mg/m3, carcinogen, 1999; Switzerland: TWA 0.1 mg/m3, carcinogen, 1999; Thailand: TWA 0.5 mg/m3, 1993; Turkey: TWA 0.5 mg (As)/m3, 1993; Turkey: TWA 0.5 mg/m3, 1993; United Kingdom: TWA 0.1 mg/m3, carcinogen, 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH: TLV: Confirmed Human Carcinogen. Russia[43] set a MAC of 0.003 mg/m3 on a daily average basis for residential areas. Several states have
set guidelines or standards for arsenic in ambient air[60]: 0.06 mg/m3 (California Prop. 65), 0.0002 μg/m3 (Rhode Island), 0.00023 μg/m3 (North Carolina), 0.024 μg/m3 (Pennsylvania), 0.05 μg/m3 (Connecticut), 0.070.39 μg/m3 (Montana), 0.67 μg/m3 (New York), 1.0 μg/m3 (South Carolina), 2.0 μg/m3 (North Dakota), 3.3 μg/m3 (Virginia), 5 μg/m3 (Nevada). Determination in Air: Use NIOSH Analytical Methods (inorganic arsenic): #7300, #7301,#7303, #7900, #9102; OSHA Analytical Methods ID-105. Permissible Concentration in Water: EPA[6] recommends a zero concentration of arsenic for human health reasons but has set a guideline of 50 μg/L[61] for drinking water. Determination in Water: See OSHA Analytical Method ID-105 for arsenic. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Absorbed through the skin. Harmful Effects and Symptoms Short Term Exposure: Potassium arsenate can affect you when breathed, and may enter through skin. Potassium arsenate is a carcinogen; handle with extreme caution. Eye contact causes irritation, burns and red, watery eyes. Skin contact can cause burning, itching, and rash. Breathing can cause irritation with sneezing and coughing. High or repeated exposures can cause disturbed sleep, with numbness and weakness of arms and legs; and can cause poor appetite; nausea, cramps, and if severe, vomiting and diarrhea. Long Term Exposure: Long-term exposure can cause ulcer or hole in the nasal septum; hoarseness and sore eyes also occur. Repeated exposure can cause nervous system damage. Repeated skin contact can cause thickened skin and/or patchy area of darkening and loss of pigment. Points of Attack: Nervous system, skin. Medical Surveillance: Before beginning employment and at regular times after that, the following are recommended: examination of the nose, skin, eyes, nails, nervous system. Test for urine arsenic (may not be accurate within 2 days of eating shellfish or fish; most accurate at the end of a workday). At NIOSH recommended exposure levels, urine arsenic should not be greater than 50100 μg/L of urine. After suspected overexposure, repeat these tests. Also, examine your skin periodically for abnormal growths. Skin cancer from arsenic is easily cured when detected early. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit.
Potassium arsenate Note to physician: For severe poisoning BAL has been used. For milder poisoning penicillamine (not penicillin) has been used, both with mixed success. Side effects occur with such treatment and it is never a substitute for controlling exposures. It can only be done under strict medical care. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Eye protection is included in the recommended respiratory protection. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: At concentrations above the NIOSH REL, or where there is no REL, at any detectable concentration: Sa (APF 5 10) (any supplied-air respirator) or SCBAF (APF 5 50) (any self-contained breathing apparatus with a full face-piece). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd,Pp (APF 5 10,000) (any self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary, self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: GmFAg100 (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or back-mounted acid gas canister having an N100, R100, or P100 filter] or SCBAE (any appropriate escapetype, self-contained breathing apparatus). Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. A regulated, marked area should be established where potassium arsenate is handled, used, or stored as required by OSHA Standard 29 CFR 1910.1018 for inorganic arsenic. Potassium arsenate must be stored to avoid contact with acids. Store in tightly closed containers in a cool, well-ventilated area. Shipping: This compound requires a shipping label of “POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 6.1 and Packing Group II. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Use HEPA vacuum or wet method to reduce dust during cleanup. Do not dry sweep. Deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream
2203
users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: Extinguish fire using an agent suitable for type of surrounding fire. Potassium arsenate itself does not burn. Poisonous gases are produced in fire, including arsenic trioxide and potassium oxide. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. References Sax, N. I. (Ed.). (1983). Dangerous Properties of Industrial Materials Report, 3, No. 4, 101103 New Jersey Department of Health and Senior Services. (October 2004). Hazardous Substances Fact Sheet: Potassium Arsenate. Trenton, NJ
Potassium arsenate
P:0860
Molecular Formula: As2HKO4 Common Formula: KAsO2 HAsO2; AsH3O3 xK Synonyms: Arsenito potasico (Spanish); Arsenous acid, potassium salt; Arsenite de potassium (French); Arsonic acid, potassium salt; Fowler’s solution (liquid); Kaliumarsenit (German); NSC 3060; Potassium metaarsenite CAS Registry Number: 13464-35-2; 1332-10-1 (solution) RTECS® Number: CG3800000 UN/NA & ERG Number: UN1678/154 EC Number: 236-680-2 [Annex I Index No.: 033-002-00-5] (potassium arsenite); 233-337-9 (potassium arsonate) Regulatory Authority and Advisory Bodies Carcinogenicity: NTP: 11th Report on Carcinogens, 2004: Known to be a human carcinogen; IARC: Human Sufficient Evidence, Animal Inadequate Evidence, 1980. Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Clean Water Act: Section 311 Hazardous Substances/RQ 40CFR117.3 (same as CERCLA, see below); Section 313 Water Priority Chemicals (57FR41331, 9/9/92). Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 500/10,000 lb (227/4540 kg) (1012450-2).
2204
Potassium arsenate
Reportable Quantity (RQ): 1 lb (0.454 kg) (10124-50-2). Arsenic compounds: Clean Air Act: Hazardous Air Pollutants (Title I, Part A, Section 112) as arsenic compounds. Clean Water Act: Toxic Pollutant (Section 401.15) as arsenic and compounds. RCRA, 40CFR261, Appendix 8 Hazardous Constituents, waste number not listed. Reportable Quantity (RQ): 1 lb (0.454 kg). EPCRA (Section 313): Includes any unique chemical substance that contains arsenic as part of that chemical’s infrastructure. Form R de minimis concentration reporting level: inorganics 0.1%; organics 1.0%. US DOT Regulated Marine Pollutant (49CFR172.101, Appendix B) as arsenates, liquid, n.o.s.; arsenates, solid, n.o.s.; arsenical pesticides liquid, toxic, flammable, n.o.s. California Proposition 65 Chemical: Cancer 2/27/87. Canada, WHMIS, Ingredients Disclosure List Concentration 1.0% as arsenic, water-soluble compounds, n.o.s. Canada: Priority Substance List & Restricted Substances/ Ocean Dumping FORBIDDEN (CEPA), National Pollutant Release Inventory (NPRI) (arsenic compounds). European/International Regulations: Hazard Symbol: T, N; Risk phrases: (as arsenic compound) R45; R23/25; R50/53; R53; Safety phrases: S1/2; S20/21; S28; S45; S60; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): 3—Highly water polluting. Description: Potassium arsenite is a white crystalline solid. Decomposes below Freezing/Melting point at 300 C. Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 0, Reactivity 0. Soluble in water. Potential Exposure: Compound Description: Agricultural Chemical; Tumorigen, Drug, Mutagen; Human Data. Potassium metaarsenite is used in veterinary medicine; and for chronic dermatitis in man. Potassium arsenite reduces silver salt to metallic silver during mirror silvering. Currently, it is probably not being used for this purpose. Incompatibilities: A weak base. Reacts with acids and decomposes on contact with strong acids producing acetic acid fumes. Arsine, a very deadly gas, can be released in the presence of acid or acid mist. Incompatible with alkaloidal salts, strong oxidizers, bromine azide, hypophosphites, sulfites in acid solution, iron salts, heavy metals and heavy metal compounds. Hydrogen gas can react with inorganic arsenic to form the highly toxic gas, arsine. Permissible Exposure Limits in Air OSHA PEL: 0.010 mg[As]/m3 TWA; cancer hazard that can be inhaled. See [1910.1018]. NIOSH REL: 0.002 mg[As]/m3 15 min Ceiling Concentration. A potential occupational carcinogen. Limit exposure to lowest feasible concentration; See Appendix A. ACGIH TLV®[1]: 0.01 mg[As]/m3 TWA; Confirmed Human Carcinogen. NIOSH IDLH: potential occupational carcinogen 5 mg [As]/m3.
Protective Action Criteria (PAC) TEEL-0: 0.0533 mg/m3 PAC-1: 2 mg/m3 PAC-2: 14 mg/m3 PAC-3: 26.7 mg/m3 DFG TRK: 0.10 mg[As]/m3; BAT: 1.30 μg[As]/L in urine/ end-of-shift; Carcinogen Category 1. Arab Republic of Egypt: TWA 0.2 mg/m3, 1993; Australia: TWA 0.05 mg/m3, carcinogen, 1993; Belgium: TWA 0.2 mg/ m3, 1993; Denmark: TWA 0.05 mg/m3, 1999; Finland: carcinogen, 1993; France: VME 0.2 mg/m3, 1993; Hungary: STEL 0.5 mg/m3, carcinogen, 1993; India: TWA 0.2 mg/m3, 1993; Norway: TWA 0.02 mg/m3, 1999; the Philippines: TWA 0.5 mg/m3, 1993; Poland: MAC (TWA) 0.01 mg/m3, 1999; Sweden: NGV 0.03 mg/m3, carcinogen, 1999; Switzerland: TWA 0.1 mg/m3, carcinogen, 1999; Thailand: TWA 0.5 mg/m3, 1993; Turkey: TWA 0.5 mg(As)/m3, 1993; Turkey: TWA 0.5 mg/m3, 1993; United Kingdom: TWA 0.1 mg/m3, carcinogen, 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH: TLV: Confirmed Human Carcinogen. Russia[43] set a MAC of 0.003 mg/m3 on a daily average basis for residential areas. Several states have set guidelines or standards for arsenic in ambient air: [60] 0.06 mg/m3 (California Prop. 65), 0.0002 μg/m3 (Rhode Island), 0.00023 μg/m3 (North Carolina), 0.024 μg/m3 (Pennsylvania), 0.05 μg/m3 3 (Connecticut), 0.070.39 μg/m (Montana), 0.67 μg/m3 (New York), 1.0 μg/m3 (South Carolina), 2.0 μg/m3 (North Dakota), 3.3 μg/m3 (Virginia), 5 μg/m3 (Nevada). Determination in Air: Use NIOSH Analytical Methods (inorganic arsenic): #7300, #7301, #7303, #7900, #9102; OSHA Analytical Methods ID-105. Permissible Concentration in Water: EPA[6] recommends a zero concentration of arsenic on a human health basis. EPA[61] has set a guideline for drinking water of 50 μg/L of arsenic. Determination in Water: See OSHA Analytical Method ID-105 for arsenic. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Absorbed through the skin. Harmful Effects and Symptoms Short Term Exposure: Irritates the eyes, skin, and respiratory tract. Skin contact can cause irritation with a burning sensation; itching. High exposure can cause loss of appetite; garlic or metallic taste; nausea, vomiting, and muscle cramps. May affect the central nervous system, digestive tract, circulatory system, causing loss of fluids and electrolytes; may cause collapse, shock, and death. Very toxic: probable oral lethal dose in humans is 50500 mg/kg, or between 1 teaspoonful and 1 oz for a 150-lb adult. Nausea, vomiting, and diarrhea result from arsenic ingestion. Patient may go into collapse and shock with weak, rapid pulse, cold sweat, coma, and death. Exposure at low level may result in death. Long Term Exposure: May cause liver damage, cirrhosis, jaundice. A skin allergen. Repeated or prolonged contact
Potassium arsenate may cause skin sensitization. Itching or skin pigmentation changes may occur. May affect the peripheral nervous system, causing weakness in the hands and feet. May cause an ulcer in the inner nose, perforation of the nasal septum, and cirrhosis. This substance is carcinogenic to humans. Chronic arsenic poisoning may manifest itself by loss of appetite; cramps, nausea, constipation, or diarrhea. Points of Attack: Liver, skin. Medical Surveillance: Liver function testing. Examination of the nervous system. Examination of the nose, eyes, nails, and skin. Test for urine arsenic. Arsenic should not be greater than 100 μg/g of creatinine in the urine. Tests are most accurate at the end of a workday and may be inaccurate within 2 days of eating shellfish. If abnormal growths are detected on the skin, they can be easily cured when detected early. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Note to physician: For severe poisoning BAL [British AntiLewisite, Dimercaprol, dithiopropanol (C3H8OS2)] has been used to treat toxic symptoms of certain heavy metals poisoning—including arsenic. Although BAL is reported to have a large margin of safety, caution must be exercised because toxic effects may be caused by excessive dosage. Most can be prevented by premedication with 1-ephedrine sulfate (CAS: 134-72-5). For milder poisoning penicillamine (not penicillin) has been used, both with mixed success. Side effects occur with such treatment and it is never a substitute for controlling exposure. It can only be done under strict medical care. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: At concentrations above the NIOSH REL, or where there is no REL, at any detectable concentration: Sa (APF 5 10) (any supplied-air respirator) or SCBAF (APF 5 50) (any self-contained
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breathing apparatus with a full face-piece). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd,Pp (APF 5 10,000) (any self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressuredemand or other positive-pressure mode in combination with an auxiliary, self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: GmFAg100 (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or backmounted acid gas canister having an N100, R100, or P100 filter] or SCBAE (any appropriate escape-type, self-contained breathing apparatus). Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. A regulated, marked area should be established where potassium arsenite is handled, used, or stored as required by OSHA Standard 29 CFR 1910.1018 for inorganic arsenic. Store in tightly closed containers in a cool, well-ventilated area away from acids, acid fumes, alkaloidal salts, strong oxidizers, bromine azide, hypophosphites, sulfites in acid solution, iron salts, heavy metals and heavy metal compounds. Where possible, automatically transfer material from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of this chemical should be grounded and bonded. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: Potassium arsenite (solid) requires a shipping label of “POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 6.1 and Packing Group II. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Avoid inhalation and skin contact. Dike far ahead of spill for later disposal. Do not touch spilled material; stop leak if you can do it without risk. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: Extinguish fire using agents suitable for surrounding fire. Potassium arsenite itself does not burn. Keep unnecessary people away; stay upwind; keep out of low areas. Wear full protective clothing and self-contained breathing apparatus. Poisonous gases are
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Potassium bromate
produced in fire, including arsenic, phosgene, and potassium oxide. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. References US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Potassium Arsenite. Washington, DC: Chemical Emergency Preparedness Program New Jersey Department of Health and Senior Services. (August 1999). Hazardous Substances Fact Sheet: Potassium Arsenite. Trenton, NJ
Potassium bromate
P:0870
Molecular Formula: BrKO3 Common Formula: KBrO3 Synonyms: Bromato potasico (Spanish); Bromic acid, potassium salt CAS Registry Number: 7758-01-2 RTECS® Number: EF8725000 UN/NA & ERG Number: UN1484/140 EC Number: 231-829-8 [Annex I Index No.: 035-003-00-6] Regulatory Authority and Advisory Bodies Carcinogenicity: IARC: Human Inadequate Evidence, animal Sufficient Evidence, possibly carcinogenic to humans, Group 2B, 1999; EPA: Likely to produce cancer in humans (inhalation, as bromates); Available data are inadequate for an assessment of human carcinogenic potential (oral route, as bromates); Limited evidence of carcinogenicity based on epidemiologic studies. Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. California Proposition 65 Chemical: Cancer 1/1/90. EPCRA Section 313 Form R de minimis concentration reporting level: 0.1%. European/International Regulations: Hazard Symbol: T, O; Risk phrases: R45; R9; R25; Safety phrases: S53; S45 (see Appendix 4). WGK (German Aquatic Hazard Class): No value assigned. Description: Potassium bromate is a white crystalline solid. Molecular weight 5 167.01; Decomposes at 370 C; Freezing/Melting point 5 350 C; also reported at 435 C. Hazard Identification (based on NFPA-704 M Rating
System): Health 2, Flammability 0, Reactivity 3 (Oxidizer). Soluble in water. Potential Exposure: Compound Description: Tumorigen, Mutagen; Human Data. Potassium bromate is used as animal feed additive, food additive; flavor and packaging material; as a laboratory reagent; and oxidizing agent. Incompatibilities: A strong oxidizer. Reacts violently with combustibles, organics, reducing agents, powdered metals, metal sulfides, carbon, sulfur, phosphorus, ammonium salts, oxidizers. Incompatible with aluminum, copper. Permissible Exposure Limits in Air AIHA WEEL: 0.1 mg/m3 TWA. Protective Action Criteria (PAC) TEEL-0: 0.1 mg/m3 PAC-1: 0.3 mg/m3 PAC-2: 60 mg/m3 PAC-3: 60 mg/m3 United Kingdom: carcinogen, 2000. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Potassium bromate can affect you when breathed in and may enter the body through the skin. Skin and eye contact can cause irritation, and burns may occur with prolonged contact. Breathing the mist or dust can irritate the nose, throat, and bronchial tubes, causing sneezing and coughing. Overexposure can cause kidney damage. Ingestion may affect the gastrointestinal tract and central nervous system. Long Term Exposure: This substance is possibly carcinogenic to humans. May affect the nervous system causing headache, irritability, impaired thinking, and personality changes. May cause kidney damage. May cause lung irritation; bronchitis may develop. Points of Attack: Lungs, kidneys, nervous system. Medical Surveillance: Before beginning employment and at regular times after that, for those with frequent or potentially high exposures, the following are recommended: lung function tests. If symptoms develop or overexposure is suspected, the following may also be useful: kidney function tests. Examination of the nervous system. Interview for brain damage. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Speed in removing material from skin is of extreme importance. Shampoo hair promptly if contaminated. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large
Potassium chlorate quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Where there is potential for exposure to potassium bromate, use a NIOSH/MSHA- or European Standard EN149-approved full-face-piece respirator equipped with particulate (dust/fume/mist) filters. Particulate filters must be checked every day before work for physical damage, such as rips or tears, and replaced as needed. Where there is potential for high exposures, use a NIOSH/MSHA- or European Standard EN149-approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuous-flow mode; or use a NIOSH/ MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—Yellow: Reactive Hazard; Store in a location separate from other materials, especially flammables and combustibles. Prior to working with this chemical you should be trained on its proper handling and storage. Potassium bromate must be stored to avoid contact with oxidizers (such as perchlorates, peroxides, permanganates, chlorates, and nitrates) and other incompatible materials listed above since violent reactions can occur. Protect storage containers against physical damage. Avoid storage on wood floors. Where possible, automatically transfer material from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of this chemical should be grounded and bonded. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. See OSHA Standard 1910.104 and NFPA 43A Code for the Storage of Liquid and Solid Oxidizers for detailed handling and storage regulations. A regulated, marked area should be established where this chemical is handled, used, or stored in compliance with OSHA Standard 1910.1045. Shipping: This compound requires a shipping label of “OXIDIZER.” It falls in Hazard Class 5.1 and Packing Group II. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered
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material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. Keep potassium bromate out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible solid. Use only water. Do not use chemical or carbon dioxide extinguishers. Poisonous gases are produced in fire, including bromine, potassium oxide, and oxygen, which increases fire hazard. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. Containers may explode in fire. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are selfcontained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positivepressure mode. References Sax, N. I. (Ed.). (1981). Dangerous Properties of Industrial Materials Report, 1, No. 7, 7071 New Jersey Department of Health and Senior Services. (July 2005). Hazardous Substances Fact Sheet: Potassium Bromate. Trenton, NJ
Potassium chlorate
P:0880
Molecular Formula: ClKO3 Common Formula: KClO3 Synonyms: Berthollet’s salt; Chlorate de potassium (French); Chlorate of potash; Chloric acid, Potassium salt; Fekabit; Kaliumchlorat (German); Oxymuriate of potash; Pearl ash; Potash chlorate; Potassium (chlorate de) (French); Potassium oxymuriate; Potcrate; Salt of tartar CAS Registry Number: 3811-04-9 RTECS® Number: FO0350000 UN/NA & ERG Number: UN2427 (solution)/140; UN1485 (solid)/140 EC Number: 223-289-7[ 017-004-00-3] Regulatory Authority and Advisory Bodies Department of Homeland Security Screening Threshold Quantity (pounds): Theft hazard 400 (Commercial grade).
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Potassium chlorate
FDA—over-the-counter drug. WGK (German Aquatic Hazard Class): 2—Hazard to waters. Description: Potassium chlorate is a white crystalline solid. Molecular weight 5 122.55; Boiling point 5 decomposes below BP at 400 C; Freezing/Melting point 5 360 C. Hazard Identification (based on NFPA-704 M Rating System): Health 2, Flammability 0, Reactivity 1 (Oxidizer). Soluble in water. Potential Exposure: Compound Description: Agricultural Chemical; Human Data. Potassium chlorate is used in the manufacture of soap, glass, pottery, and many potassium salts; as an oxidizing agent, in explosives, matches, textile printing; disinfectants, and bleaching. Incompatibilities: A strong oxidizer. Decomposes on heating above 400 C, on contact with strong acids producing toxic fumes including chlorine dioxide, chlorine fumes, and oxygen. Violent reaction with combustibles, oxidizers, strong acids, and reducing materials. Attacks many metals in the presence of water. Permissible Exposure Limits in Air Protective Action Criteria (PAC) TEEL-0: 12.5 mg/m3 PAC-1: 40 mg/m3 PAC-2: 300 mg/m3 PAC-3: 350 mg/m3 Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Potassium chlorate can affect you when breathed in. Irritates the eyes, skin, and respiratory tract. Prolonged contact can cause eye and skin burns and possible permanent damage. Exposure lowers the ability of the blood to carry oxygen (methemoglobinemia). This can result in a bluish color to skin and lips, headache, dizziness, collapse, and even death. Breathing the dust or mist can cause nose and throat irritation with sneezing, coughing, and sore throat. High exposure may cause kidney damage. Long Term Exposure: May cause lung damage; bronchitis may develop. Repeated exposures may affect the kidneys and central nervous system. Points of Attack: Lungs, kidneys, nervous system. Medical Surveillance: Before beginning employment and at regular times after that, for those with frequent or potentially high exposures, the following are recommended: lung function tests. If symptoms develop or overexposure is suspected, the following may be useful: A blood test for methemoglobin level. Kidney function tests. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Speed in removing material from skin is of extreme importance. Shampoo hair promptly if contaminated. Seek medical attention immediately. If this
chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Note to physician: Treat for methemoglobinemia. Spectrophotometry may be required for precise determination of levels of methemoglobin in urine. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Where there is potential for exposures to potassium chlorate, use a NIOSH/MSHA- or European Standard EN149-approved full-face-piece respirator equipped with particulate (dust/fume/mist) filters. Particulate filters must be checked every day before work for physical damage, such as rips or tears, and replaced as needed. Where there is potential for high exposures, use a NIOSH/MSHA- or European Standard EN149-approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuous-flow mode; or use a NIOSH/ MSHA- or European Standard EN149-approved selfcontained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—Yellow: Reactive Hazard; Store in a location separate from other materials, especially flammables and combustibles. Prior to working with this chemical you should be trained on its proper handling and storage. Potassium chlorate must be stored to avoid contact with oxidizers (such as perchlorates, peroxides, permanganates, chlorates, and nitrates) and strong acids (such as hydrochloric, sulfuric, and nitric); since violent reactions occur. Protect storage containers from physical damage. Avoid storage on wood floors. Where possible, automatically transfer material from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of this chemical should be grounded and bonded. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. See OSHA Standard 1910.104 and NFPA 43A Code for the Storage of Liquid and Solid Oxidizers for detailed handling and storage regulations.
Potassium chloroplatinates Shipping: Potassium chlorate requires a shipping label of “OXIDIZER.” It falls in Hazard Class 5.1 and Packing Group II. Potassium chlorate, aqueous solution, requires a shipping label of “OXIDIZER.” It falls in Hazard Class 5.1 and Packing Group II or III. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible solid. Use water spray only. Do not use dry chemical, halon, foam, or carbon dioxide extinguishers. Poisonous gases are produced in fire. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Reference New Jersey Department of Health and Senior Services. (October 2004). Hazardous Substances Fact Sheet: Potassium Chlorate. Trenton, NJ
Potassium chloroplatinates
P:0890
Molecular Formula: Cl4K2Pt (tetra-); Cl6K2Pt (hexa-) Common Formula: K2PtCl4; K2PtCl6 Synonyms: tetra-: Dipotassium tetrachloroplatinate; Potassium tetrachloroplatinate(II); Tetrachlorodipotassium platinate hexa-: Dipotassium hexachloroplatinate; Hexachlorodipotassium platinate; Hexachloroplatinate(2-) dipotassium; Platinic potassium chloride; Potassium chloroplatinate; Potassium hexachloroplatinate(IV); Potassium hexachloroplatinate(4 1 ); Potassium platinic chloride CAS Registry Number: 16921-30-5 (hexa-); 10025-99-7 (tetra-) RTECS® Number: PT1650000 (hexa-); TP1850000 (tetra-)
2209
UN/NA & ERG Number: UN3290 [Toxic solid, corrosive, inorganic, n.o.s., (Platinium (IV) potassium chloride)]/154 EC Number: 240-979-3 [Annex I Index No.: 078-007-00-3] (dipotassium hexachloroplatinate); 233-050-9 [Annex I Index No.: 078-004-00-7] (dipotassium tetrachloroplatinate) Regulatory Authority and Advisory Bodies Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Canada, WHMIS, Ingredients Disclosure List Concentration 0.1%. European/International Regulations (hexa-): Hazard Symbol: T; Risk phrases: R25; R41; R42/43; Safety phrases: S1/2; S22; S26; S36/37/39; S53; S45; (tetra-): Hazard Symbol: T; Risk phrases: R25; R38; R41; R42/43; Safety phrases: S2; S22; S26; S36/37/39; S45 (see Appendix 4). WGK (German Aquatic Hazard Class): No value assigned. Description: Potassium tetrachloroplatinate(II), K2PtCl4 is a ruby-red crystalline solid and Potassium hexachloroplatinate (IV), K2PtCl6 is an orange-yellow solid. Molecular weight 5 485.89 (hexa-); 415.09 (tetra-); Freezing/Melting point 5 (decomposes) at 250 C (hexa-). Hazard Identification (based on NFPA-704 M Rating System): (hexa-) Health 3, Flammability 0, Reactivity 0. Soluble in water. Potential Exposure: These materials are used in photography. Permissible Exposure Limits in Air OSHA PEL: 0.002 mg[Pt]/m3 TWA NIOSH REL: 0.002 mg[Pt]/m3 TWA ACGIH TLV®[1]: 1 0.002 mg[Pt]/m3 TWA NIOSH IDLH: 4 mg [Pt]/m3 No TEEL available DFG MAK: No numerical value established. Data may be available; however, 2 μg[Pt]/m3 peak should not be exceeded; danger of skin and airway sensitization, as chloroplatinates. Several states have set guidelines or standards for platinum in ambient air[60] ranging from 0.1 μg/m3 (Nevada) to 0.420.0 μg/m3 (Connecticut) to 10.0 μg/m3 (North Dakota) to 330.0 μg/m3 (Virginia). Determination in Air: Use NIOSH II(7) Method #S-19 (soluble salts) Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Potassium chloroplatinates can affect you when breathed in. Severe allergy can develop to potassium chloroplatinates. Symptoms include asthma (with cough, wheezing, and/or shortness of breath), runny nose, and/or skin rash, sometimes with hives. If allergy develops, even small future exposure can trigger significant symptoms. Some persons exposed to this type of chemical have developed lung scarring. Family members can develop allergy to dust carried home on work clothing. It may irritate the eyes, nose, and throat. High exposure may cause irritability and even seizures.
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Potassium chloroplatinates
Long Term Exposure: May cause skin sensitization and dermatitis and/or asthma-like allergy. Tetrachloroplatinates are mutagens. Points of Attack: Skin, lungs. Medical Surveillance: Before beginning employment and at regular times after that, the following are recommended. Lung function tests. These may be normal if the person is not having an attack at the time of the test. If symptoms develop or overexposure is suspected, the following may be useful: chest X-ray every 3 years should be considered if above tests are not normal. Evaluation by a qualified allergist, including careful exposure history and special testing, may help diagnose skin allergy. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: (for soluble Pt salts): Up to 0.05 mg/m3: Sa:Cf* (APF 5 25) (any supplied-air respirator operated in a continuous-flow mode). Up to 0.1 mg/m3: 100F (APF 5 50) (any air-purifying, full-face-piece respirator with an N100, R100, or P100 filter) or SCBAF (APF 5 50) (any self-contained breathing apparatus with a full face-piece) or SaF (APF 5 50) (any supplied-air respirator with a full face-piece). Up to 4 mg/m3: SaF: Pd,Pp (APF 5 2000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd, Pp (APF 5 10,000) (any NIOSH/MSHA- or European Standard EN 149-approved self-contained breathing apparatus that has a full face-piece and is operated in a pressuredemand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that
has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary, self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: 100 F (APF 5 50) (any air-purifying, full-face-piece respirator with an N100, R100, or P100 filter) or SCBAE (any appropriate escape-type, self-contained breathing apparatus). * Substance cause eye irritation and damage; eye protection needed. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, wellventilated area. Shipping: Toxic solid, corrosive, inorganic, n.o.s., (Platinium (IV) potassium chloride) requires a shipping label of “POISONOUS/TOXIC MATERIALS, CORROSIVE.” It falls in DOT/UN Hazard Class 6.1 and Packing Group II. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: These chemicals may burn but do not readily ignite. Use dry chemical, carbon dioxide, water spray, or foam extinguishers. Poisonous gases are produced in fire, including chlorides and potassium oxide. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. References New Jersey Department of Health and Senior Services. (March 2001). Hazardous Substances Fact Sheet: Potassium Tetrachloroplatinate. Trenton, NJ New Jersey Department of Health and Senior Services. (June 2002). Hazardous Substances Fact Sheet: Potassium Hexachloroplatinate. Trenton, NJ
Potassium chromate
Potassium chromate
P:0900
Molecular Formula: CrK2O4; Cr2K2O7 Common Formula: K2CrO4; K2Cr2O7 Synonyms: chromate: Bipotassium chromate; Chromate of potassium; Dipotassium chromate; Dipotassium monochromate; Neutral potassium chromate; Potassium chromate (VI); Tarapacaite dichromate: Bichromate of potash; Chromic acid, dipotassium salt; Dipotassium dichromate; Iopezite; Kaliumdichromat (German); Potassium bichromate; Potassium dichromate(VI) CAS Registry Number: 7789-00-6; 7778-50-9 (dichromate) RTECS® Number: GB2940000 (chromate); HX7680000 (dichromate) UN/NA & ERG Number: UN1479/140 EC Number: 232-140-5 [Annex I Index No.: 024-006-00-8]; 231-906-6 [Annex I Index No.: 024-002-00-6] (dichromate) Regulatory Authority and Advisory Bodies Carcinogenicity: IARC: Human Sufficient Evidence; Animal Sufficient Evidence, carcinogenic to humans, Group 1, 1997; NTP: 11th Report on Carcinogens, 2004: Known to be a human carcinogen. US EPA Gene-Tox Program, Positive: SHE—clonal assay; In vitro cytogenetics—nonhuman; Positive: B. subtilis rec assay; Positive: CHO gene mutation (dichromate). US EPA, FIFRA, 1998 Status of Pesticides: Supported. Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Canada, WHMIS, Ingredients Disclosure List Concentration 1.0% as chromate; 0.1% as dichromate. Water Pollution Standard Proposed (EPA).[6] Hazardous Substance (EPA) (RQ 5 1000/454).[4] Priority Toxic Pollutant (EPA).[6] As chromium compounds: Clean Air Act: Hazardous Air Pollutants (Title I, Part A, Section 112). Clean Water Act: Toxic Pollutant (Section 401.15); 40CFR401.15 Section 307 Toxic Pollutants as chromium and compounds. RCRA, 40CFR261, Appendix 8 Hazardous Constituents, waste number not listed. Canada, WHMIS, Ingredients Disclosure List Concentration 0.1%. European/International Regulations (chromate): Hazard Symbol: T1, N; Risk phrases: R49; R46; R36/37/38; R43; R50/53; Safety phrases: S53; S45; S60; S61; (dichromate). Hazard Symbol: T1, N; Risk phrases: R45; R46; R60; R61; R8; R21; R25; R26; R34; R42/43;R48/23; R50/53; Safety phrases: S53; S45; S60; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): No value assigned. Description: Potassium chromate(VI) is a yellow crystalline solid. Molecular weight 5 194.20; Freezing/Melting point 5 971 C. Soluble in water. Potassium dichromate(VI) is a yellowish-red crystalline solid. Molecular
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weight 5 294.20; Boiling point 5 decomposition at 500 C; Freezing/Melting point 5 398 C. Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 0, Reactivity 3 (Oxidizer). Soluble in water. Potential Exposure: Compound Description: Tumorigen, Mutagen; Reproductive Effector; Human Data; Natural Product; Primary Irritant. Potassium chromate is used in printing, photomechanical processing, chrome-pigment production, and wool preservative methods; to make dyes, pigments, inks, and enamels; as an oxidizing agent, analytical reagent; in electroplating, explosives. Incompatibilities: A powerful oxidizer. Violent reactions with combustibles, organics, powdered metals, or easily oxidizable substances. Contact with hydrazine causes explosion. Permissible Exposure Limits in Air Protective Action Criteria (PAC) TEEL-0: 0.0187 mg/m3 PAC-1: 2 mg/m3 PAC-2: 12.5 mg/m3 PAC-3: 56 mg/m3 OSHA PEL: 0.1 mg[CrO3]/m3 Ceiling Concentration. NIOSH REL: 0.001mg[CrO3]/m3 TWA, potential carcinogen, limit exposure to lowest feasible level. NIOSH considers all Cr(VI) compounds (including chromic acid; tert-butyl chromate; zinc chromate; and chromyl chloride) to be potential occupational carcinogens. ACGIH TLV®[1]: 0.05 mg[Cr]/m3 TWA, Confirmed Human Carcinogen; BEI issued. DFG MAK: Danger of skin sensitization; Carcinogen Category 2; TRK: 0.05 mg[Cr]/m3; 20 μg/L [Cr] in urine at end-of-shift. NIOSH IDLH: 15 mg[Cr(VI)]/m3. United Kingdom: carcinogen, 2000; the former USSRUNEP/IRPTC joint project[43] give a MAC of 0.01 mg/m3 in work-place air. Connecticut[60] has set a guideline of 0.25 μg/m3 for chromium trioxide in ambient air; Sweden[35] for potassium chromate at 0.02 mg/m3 as a TWA in work-place air. North Carolina[60] has set a guideline of zero for ambient air for both compounds. 7778-50-9 (dichromate) Protective Action Criteria (PAC) TEEL-0: 0.0141 mg/m3 PAC-1: 4 mg/m3 PAC-2: 30 mg/m3 PAC-3: 42.4 mg/m3 Determination in Air: Use NIOSH Analytical Methods #7600, 7604, 7605, 7703, 9101 and OSHA Analytical Methods ID-103, ID-215, W-4001. Permissible Concentration in Water: The EPA[6] has designated chromium as a priority toxic pollutant. To protect human health, the limits are trivalent chromium (in chromates): 170 μg/L and hexavalent chromium (in dichromates) 50 μg/L. Determination in Water: Total chromium may be determined by digestion followed by atomic absorption, or by
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Potassium chromate
colorimetry (diphenylcarbazide), or by inductively coupled plasma (CP) optical emission spectrometry. Chromium (VI) may be determined by extraction and atomic absorption or colorimetry (using diphenylhydrazide). Dissolved total Cr or Cr(VI) may be determined by 0.45 μm filtration followed by the above-cited methods.[49] Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Potassium chromates can affect you when breathed in. It can also pass into inner layers of the skin. Eye contact can cause severe damage with possible loss of vision. Irritation of nose, throat, and bronchial tubes can occur, with cough and/or wheezing. Skin contact can cause severe irritation, deep ulcers, or an allergic skin rash. Long Term Exposure: Potassium chromate is a human carcinogen. Potassium chromates can cause a sore or perforated nasal septum; with bleeding, discharge or crusting. May cause skin allergy. Can cause lung irritation; bronchitis may develop. Points of Attack: Lungs, skin. Medical Surveillance: NIOSH lists the following tests: Blood gas analysis, complete blood count; chest X-ray, electrocardiogram, liver function tests; pulmonary function tests; sputum cytology, urine (chemical/metabolite), urinalysis (routine), white blood cell count/differential. Before beginning employment and at regular times after that, for those with frequent or potentially high exposures, the following are recommended: examination of the nose and skin. If symptoms develop or overexposure is suspected, the following may be useful: evaluation by a qualified allergist, including careful exposure history and special testing, may help diagnose skin allergy. Also, check your skin daily for little bumps or blisters, the first sign of “chrome ulcers.” If not treated early, these can last for years after exposure. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Prevent skin contact. (As chromic acid and chromates) 8 h (more than 8 h of resistance to breakthrough .0.1 μg/ cm/min): polyethylene gloves, suits, boots; polyvinyl chloride gloves, suits, boots; Saranex™ coated suits; 4 h (At least 4 but ,8 h of resistance to breakthrough .0.1 μg/cm2/ min): butyl rubber gloves, suits, boots; Viton™ gloves, suits.
Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation, For potassium dichromate, Neoprene™ and polyvinyl chloride are among the recommended protective materials. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: NIOSH, as chromates: at any concentrations above the NIOSH REL, or where there is no REL, at any detectable concentration: SCBAF: Pd,Pp (APF 5 10,000) (any self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary, self-contained breathing apparatus operated in a pressuredemand or other positive-pressure mode). Escape: 100F (APF 5 50) (any air-purifying, full-face-piece respirator with an N100, R100, or P100 filter) or SCBAE (any appropriate escape-type, self-contained breathing apparatus). Storage: Color Code—Yellow: Reactive Hazard; Store in a location separate from other materials, especially flammables and combustibles. Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Potassium chromates must be stored to avoid contact with combustible, organic, or other easily oxidized materials (such as paper, wood, sulfur, aluminum, hydrazine, and plastics) since violent reactions occur. A regulated, marked area should be established where potassium chromate is handled, used, or stored. Where possible, automatically transfer material from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of this chemical should be grounded and bonded. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. See OSHA Standard 1910.104 and NFPA 43A Code for the Storage of Liquid and Solid Oxidizers for detailed handling and storage regulations. A regulated, marked area should be established where this chemical is handled, used, or stored in compliance with OSHA Standard 1910.1045. Shipping: Oxidizing solid, n.o.s. requires a shipping label of “OXIDIZER.” They fall in DOT Hazard Class 5.1 and Packing Group II or III. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in
Potassium cyanide sealed containers. Ventilate area after cleanup is complete. Keep potassium dichromate out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical may burn but does not easily ignite. Use dry chemical, carbon dioxide, water spray, or foam extinguishers. Poisonous gases are produced in fire, including chromium and potassium oxides. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. References Sax, N. I. (Ed.). Dangerous Properties of Industrial Materials Report, 1, No. 7, 7173 (1981) and 8, No. 5, 8694 (1988) (Potassium Chromate) New Jersey Department of Health and Senior Services. (September 1996). Hazardous Substances Fact Sheet: Potassium Dichromate. Trenton, NJ New Jersey Department of Health and Senior Services. (June 2003). Hazardous Substances Fact Sheet: Potassium Chromate. Trenton, NJ
Potassium cyanide
P:0910
Molecular Formula: CNK Common Formula: KCN Synonyms: Cianuro potasico (Spanish); Cyanide of potassium; Cyanure de potassium (French); Hydrocyanic acid, Potassium salt; Kalium-cyanid (German) CAS Registry Number: 151-50-8 RTECS® Number: TS8750000 UN/NA & ERG Number: UN1680/157 EC Number: 205-793-3 Regulatory Authority and Advisory Bodies Department of Homeland Security Screening Threshold Quantity (pounds): Sabotage/Contamination Hazard: A placarded amount (commercial grade).
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Clean Water Act: Section 311 Hazardous Substances/RQ 40CFR117.3 (same as CERCLA, see below); Section 313 Water Priority Chemicals (57FR41331, 9/9/92). US EPA Hazardous Waste Number (RCRA No.): P098. RCRA, 40CFR261, Appendix 8 Hazardous Constituents. Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 100 lb (45.4 kg). Reportable Quantity (RQ): 10 lb (4.54 kg). US DOT Regulated Marine Pollutant (49CFR172.101, Appendix B). Canada, National Pollutant Release Inventory (NPRI); CEPA Priority Substance List, Ocean dumping prohibited. As cyanide compounds: Clean Air Act: Hazardous Air Pollutants (Title I, Part A, Section 112). Clean Water Act: 40CFR423, Appendix A, Priority Pollutants, as cyanide, total. US EPA Hazardous Waste Number (RCRA No.): P030 as cyanides soluble salts and complexes, n.o.s. RCRA, 40CFR261, Appendix 8 Hazardous Constituents. as cyanides, soluble salts and complexes, n.o.s. Canada, WHMIS, Ingredients Disclosure List Concentration 1.0% as cyanide compounds, inorganic, n.o.s. WGK (German Aquatic Hazard Class): 3—Severe hazard to waters. Description: Potassium cyanide is available as white lumps, granular powder, or colorless solution. It may be shipped as capsules, tablets, or pellets. Toxic hydrogen cyanide gas released by potassium cyanide has a distinctive, mild, bitter almond odor, but many people cannot detect it; the odor does not provide adequate warning of hazardous concentrations. Molecular weight 5 65.12; Specific gravity (H2O:1) 5 1.55 at 20 C; Boiling point 5 1625 C; Freezing/ Melting point 5 633.9 C. Hazard Identification (based on NFPA-704 M Rating System): Health 4, Flammability 0, Reactivity 0. Soluble in water; solubility 5 72% at 25 C. Potential Exposure: Compound Description: Organometallic, Mutagen; Reproductive Effector; Human Data. Used in electroplating, steel hardening, extraction of precious metals form ores, as a fumigant, in insecticides, a reagent in analytical chemistry. Incompatibilities: Potassium cyanide decomposes on contact with water, humidity, carbon dioxide, strong acids (such as hydrochloric, sulfuric, and nitric acids), and acid salts, producing highly toxic and highly flammable hydrogen cyanide gas. Potassium cyanide absorbs water from air (is hygroscopic or deliquescent); the aqueous solution is a strong base. Incompatible with organic anhydrides, isocyanates, alkylene oxides, epichlorohydrin, aldehydes, alcohols, glycols, phenols, cresols, caprolactum, strong oxidizers, nitrogen trichloride, sodium chlorate. Attacks aluminum, copper, zinc in the presence of moisture. Permissible Exposure Limits in Air OSHA PEL: 5 mg[CN]/m3/4.7 ppm TWA. NIOSH REL: 5 mg[CN]/m3/4.7 ppm/10 min Ceiling Concentration.
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Potassium cyanide
ACGIH TLV®[1]: 5 mg[CN]/m3 [skin] Ceiling Concentration. Protective Action Criteria (PAC)* TEEL-0: 5.3 mg/m3 PAC-1: 5.3 mg/m3 PAC-2: 19 mg/m3 PAC-3: 40 mg/m3 *AEGLs (Acute Emergency Guideline Levels) & ERPGs (Emergency Response Planning Guideline) are in bold face. DFG MAK: 2 mg[CN]/m3 , inhalable fraction TWA; Peak Limitation Category II(1) [skin]; Pregnancy Risk Group: C. NIOSH IDLH: 25 mg[CN]/m3. Skin contact may contribute significantly in overall exposure. Australia: TWA 5 mg/m3, [skin], 1993; Austria: MAK 5 mg [CN]/m3, [skin], 1999; Denmark: TWA 5 mg/m3, [skin], 1999; France: VME 5 mg[CN]/m3, [skin], 1999; Poland: TWA 0.3 mg[CN]/m3, ceiling 10 mg[CN]/m3, 1999; Switzerland: MAK-W 5 mg/m3, KZG-W 10 mg/m3, [skin], 1999; United Kingdom: TWA 5 mg[CN]/m3, [skin], 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: Ceiling Concentration 5 mg/m3 [skin]. Russia[43] has set a MAC value of 0.009 mg/m3 for ambient air in residential areas on a momentary basis and 0.004 mg/m3 on a daily average basis. Several states have set guidelines or standards for cyanides in ambient air[60] ranging from 16.7 μg/m3 (New York) to 50.0 μg/m3 (Florida and North Dakota) to 80.0 μg/ m3 (Virginia) to 100 μg/m3 (Connecticut and South Dakota) to 125 μg/m3 (South Carolina) to 119.0 μg/m3 (Nevada). Determination in Air: Use NIOSH Analytical Method (IV) #7904, Cyanides. See also Method #6010, Hydrogen cyanide.[18] Permissible Concentration in Water: In 1976 the EPA criterion was 5.0 μg/L for freshwater and marine aquatic life and wildlife. As of 1980, the criteria are: To protect freshwater aquatic life: 3.5 μg/L as a 24-h average, never to exceed 52.0 μg/L. To protect saltwater aquatic life: 30.0 μg/L on an acute toxicity basis; 2.0 μg/L on a chronic toxicity basis. To protect human health: 200 μg/L. The allowable daily intake for man is 8.4 mg/day.[6] On the international scene, the South African Bureau of Standards has set 10 μg/L, the World Health Organization (WHO) 10 μg/L, and Germany 50 μg/L as drinking water standards. Other international limits[35] include an EEC limit of 50 μg/ L; Mexican limits of 200 μg/L in drinking water and 1.0 μg/ L in coastal waters; and a Swedish limit of 100 μg/L. Russia[43] set a MAC of 100 μg/L in water bodies used for domestic purposes and 50 μg/L in water for fishery purposes. The US EPA[49] has determined a no-observedadverse-effect-level (NOAEL) of 10.8 mg/kg/day which yields a lifetime health advisory of 154 μg/L. States which have set guidelines for cyanides in drinking water[61] include Arizona at 160 μg/L and Kansas at 220 μg/L. Determination in Water: Distillation followed by silver nitrate titration or colorimetric analysis using pyridine pyrazolone (or barbituric acid).
Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Absorbed through the skin. Harmful Effects and Symptoms Short Term Exposure: Potassium cyanide is corrosive to the eyes, skin, and the respiratory tract. Contact can cause skin and eye burns, and possible permanent eye damage. Inhalation can cause lung irritation with coughing, sneezing, and difficult breathing; slow gasping respiration. Corrosive if swallowed. These substances may affect the central nervous system. Symptoms include headaches, confusion, nausea, pounding heart, weakness, unconsciousness, and death. Long Term Exposure: Repeated or prolonged contact with potassium cyanide may cause thyroid gland enlargement and interfere with thyroid function. May cause nosebleed and sores in the nose; changes in blood cell count. May cause central nervous system damage with headache, dizziness, confusion; nausea, vomiting, pounding heart, weakness in the arms and legs, unconsciousness, and death. May affect liver and kidney function. Points of Attack: Liver, kidneys, skin, cardiovascular system, central nervous system, thyroid gland. Medical Surveillance: Consider the points of attack in preplacement and periodic physical examinations. Urine thiocyanate levels. Blood cyanide levels. Complete blood count (CBC). Evaluation of thyroid function. Liver function tests. Kidney function tests. Central nervous system tests. EKG. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Speed in removing material from skin is of extreme importance. Shampoo hair promptly if contaminated. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Keep under observation for 2448 h as symptoms may return. Use amyl nitrate capsules if symptoms develop. All area employees should be trained regularly in emergency measures for cyanide poisoning and in CPR. A cyanide antidote kit should be kept in the immediate work area and must be rapidly available. Kit ingredients should be replaced every 12 years to ensure freshness. Persons trained in the use of this kit, oxygen use, and CPR must be quickly available. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be
Potassium cyanide worn when working with this chemical. Wear splash-proof chemical goggles and face shield when working with liquid unless full face-piece respiratory protection is worn. Wear dust-proof goggles and face shield when working with powders or dust unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: When used as a weapon, use SCBA Respirator Certified By NIOSH For CBRN Environments. Up to 25 mg/m3: Sa (APF 5 10) (any supplied-air respirator) or SCBAF (APF 5 50) (any self-contained breathing apparatus with full face-piece). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd,Pp (APF 5 10,000) (any self-contained breathing apparatus that has a full face-piece and is operated in a pressuredemand or other positive-pressure mode) or Sa: Pd,Pp (APF 5 1000): ASCBA (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: GmFS100 (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or backmounted canister providing protection against the compound of concern and having an N100, R100, or P100 filter] or SCBAE (any appropriate escape-type, self-contained breathing apparatus). Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Before entering confined space where this chemical may be present, check to make sure that an explosive concentration does not exist. Note to physician: For severe poisoning BAL [British Anti-Lewisite, Dimercaprol, dithiopropanol (C3H8OS2)] has been used to treat toxic symptoms of certain heavy metals poisoning—including arsenic. Although BAL is reported to have a large margin of safety, caution must be exercised because toxic effects may be caused by excessive dosage. Most can be prevented by premedication with 1-ephedrine sulfate (CAS: 134-72-5). For milder poisoning penicillamine (not penicillin) has been used, both with mixed success. Side effects occur with such treatment and it is never a substitute for controlling exposure. It can only be done under strict medical care. Note to physician: For severe poisoning BAL [British Anti-Lewisite, Dimercaprol, dithiopropanol (C3H8OS2)] has been used to treat toxic symptoms of certain heavy metals poisoning—including arsenic. Although BAL is reported to have a large margin of safety, caution must be exercised because toxic effects may be caused by excessive dosage. Most can be prevented by premedication with 1-ephedrine sulfate (CAS: 134-72-5). For milder poisoning penicillamine (not penicillin) has been used, both with mixed success. Side effects occur with such treatment and it is never a substitute for controlling exposure. It can only be done under strict medical care.
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Store in tightly closed containers in a cool, well-ventilated area away from strong acids, acid salts, oxidizers, light, and moisture. Where possible, automatically transfer material from drums or other storage containers to process containers. Shipping: Potassium cyanide require a shipping label of “POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 6.1 and in Packing Group I. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. This chemical has a lower explosive limit; ventilate closed spaces before entering them. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Initial isolation and protective action distances: Distances shown are likely to be affected during the first 30 min after materials are spilled and could increase with time. If more than one tank car, cargo tank, portable tank, or large cylinder involved in the incident is leaking, the protective action distance may need to be increased. You may need to seek emergency information from CHEMTREC at (800) 4249300 or seek professional environmental engineering assistance from the US EPA Environmental Response Team at (908) 548-8730 (24-h response line). UN 1680 (Potassium cyanide) is on the DOT’s list of dangerous water-reactive materials which create large amounts of toxic vapor when spilled in water: Dangerous from 0.5 to 10 km (0.36.0 miles) downwind. Fire Extinguishing: KCN is not combustible itself but it decomposes in the presence of moisture, damp air, or carbon dioxide, producing highly toxic and flammable hydrogen cyanide gas and oxides of nitrogen. NO acidic dry chemical extinguishers. NO hydrous agents. NO water. NO carbon dioxide. Use dry chemical and foam on surrounding fires. Vapors are heavier than air and may collect in low areas. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. Do not allow water to enter open containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA
2216
Potassium dichloro-isocyanurate
1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant ($100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. In accordance with 40CFR165, follow recommendations for the disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by contacting your local or federal environmental control agency or by contacting your regional EPA office. Add strong alkaline hypochlorite and react for 24 h. Then flush to sewer with large volumes of water.[22] Reference New Jersey Department of Health and Senior Services. (August 2005). Hazardous Substances Fact Sheet: Potassium Cyanide. Trenton NJ
Potassium dichloroisocyanurate
P:0920
Molecular Formula: C3Cl2KN3O3 Common Formula: KCl2(NCO)3 Synonyms: ACL-59; Dichloroisocyanuric acid, potassium salt; Dichloro-s-triazine-2,4,6(1H,3H,5H)-trione potassium deriv; 1,3-Dichloro-s-triazine-2,4,6(1H,3H,5H)trione potassium salt; Dichlor-s-triazin-2,4,6(1H,3H,5H)trione potassium; Isocyanuric acid, dichloro-, potassium salt; Potassium dichloro-s-triazinetrione; Potassium troclosene; s-Triazine2,4,6(1H,3H,5H)-trione, dichloro-, potassium deriv; 1,3,5Triazine-2,4,6(1H,3H,5H)-trione, 1,3-dichloro-, potassium salt; Troclosene potassium CAS Registry Number: 2244-21-5 RTECS® Number: XZ1850000 UN/NA & ERG Number: UN2465 (Dichloroisocyanuric acid salts)/140 EC Number: 218-828-8 [Annex I Index No.: 613-030-00-X] Regulatory Authority and Advisory Bodies Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: Hazard Symbol: Xn, N; Risk phrases: R22; R31; R36/37; R50/53; Safety phrases: S2; S8; S26; S41; S60; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): No value assigned. Description: Potassium dichloroisocyanurate is a white crystalline solid with a chlorine odor. Molecular weight 5 237.07; Freezing/Melting point 5 (decomposes) 250 C. Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 0, Reactivity 2. Oxidizer. Reacts with water; Slightly soluble; solubility5 1050 mg/mL at 20 C.[NTP]
Potential Exposure: Potassium dichloroisocyanurate is used in household bleaches, dishwashing compounds, and detergents. Incompatibilities: A strong oxidizer; violent reaction with reducing agents, combustibles, organics, easily chlorinated or oxidized materials, ammonia, urea, other nitrogen compounds, calcium hypochloride, other alkalies, and moisture. Permissible Exposure Limits in Air No standards or TEEL available. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Potassium dichloroisocyanurate can affect you when breathed in. Exposure can severely irritate the eyes. It can also irritate the nose, throat, and air passages. Contact can cause skin and eye irritation. Long Term Exposure: May cause lung irritation and damage. Points of Attack: Lungs, skin. Medical Surveillance: Before beginning employment and at regular times after that, for those with frequent or potentially high exposures, the following is recommended: lung function tests. consider chest X-ray following acute overexposure. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Where there is potential for exposure to potassium dichloroisocyanurate, use a NIOSH/MSHA- or European Standard EN149-approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuous-flow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing
Potassium ferrocyanide apparatus with a full face-piece operated in a pressuredemand or other positive-pressure mode. Storage: Color Code—Yellow: Reactive Hazard; Store in a location separate from other materials, especially flammables and combustibles. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, well-ventilated area away from combustibles (like wood, paper, and oil), ammonia, urea, other nitrogen compounds, calcium hypochlorite, other alkalis, and moisture. Do not store on wooden floors. Where possible, automatically transfer material from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of this chemical should be grounded and bonded. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. See OSHA Standard 1910.104 and NFPA 43A Code for the Storage of Liquid and Solid Oxidizers for detailed handling and storage regulations. Shipping: Dichloroisocyanuric acid, dry requires a shipping label of “OXIDIZER.” It falls in Hazard Class 5.1 and Packing Group II. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. Do not use water. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: Potassium dichloroisocyanurate is not flammable. Potassium dichloroisocyanurate is a strong oxidizer and a dangerous fire hazard on contact with combustibles (such as wood, paper, and oil). Poisonous gases are produced in fire, including chlorine gas, potassium oxide, and oxides of nitrogen. Use dry chemical, or CO2 extinguishers. Use water to keep fire-exposed containers cool. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode.
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Reference New Jersey Department of Health and Senior Services. (May 2002). Hazardous Substances Fact Sheet: Potassium Dichloroisocyanurate. Trenton, NJ
Potassium ferrocyanide
P:0930
Molecular Formula: C6K4N6Fe Common Formula: K4Fe(CN)6 Synonyms: Ferrate(4-), hexacyano-, tetrapotassium; Ferrate (4-), hexakis(cyano-C)-, tetrapotassium, (OC-6-11)-; Potassium ferrocyanate; Potassium ferrocyanide; Potassium hexacyanoferrate; Potassium hexacyanoferrate(II); Tetrapotassium ferrocyanide; Tetrapotassium hexacyanoferrate; Tetrapotassium hexacyanoferrate(II); Tetrapotassium hexacyanoferrate(4-) CAS Registry Number: 13943-58-3 RTECS® Number: LI8219000 UN/NA & ERG Number: Not regulated. EC Number: 237-722-2 Regulatory Authority and Advisory Bodies Clean Air Act: Hazardous Air Pollutants (Title I, Part A, Section 112). Clean Water Act: 40CFR423, Appendix A, Priority Pollutants as cyanide, total. US EPA Hazardous Waste Number (RCRA No.): P030 as cyanides soluble salts and complexes, n.o.s. RCRA, 40CFR261, Appendix 8 Hazardous Constituents. as cyanides, soluble salts and complexes, n.o.s. EPCRA (Section 313): X 1 CN2 where X 5 H1 or any other group where a formal dissociation may occur. For example, KCN or Ca(CN)2. Form R de minimis concentration reporting level: 1.0%. US DOT Regulated Marine Pollutant (49CFR172.101, Appendix B) as cyanide mixtures, cyanide solutions or cyanides, inorganic, n.o.s. Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%; National Pollutant Release Inventory (NPRI); CEPA Priority Substance List, Ocean dumping prohibited. WGK (German Aquatic Hazard Class): 2—Hazard to waters. Description: Tetrapotassium hexacyanoferrate is a lemonyellow crystalline solid. Molecular weight 5 368.37; Boiling point 5 (decomposes). Hazard Identification (based on NFPA-704 M Rating System): Health 1, Flammability 0, Reactivity 2. Potential Exposure: Used in dyeing, tempering steel, explosives, process engraving, and lithography. Incompatibilities: Acids or acid fumes may cause release of highly toxic cyanide fumes. Reacts violently with ammonia, copper nitrate; sodium nitrite or chromate. Permissible Exposure Limits in Air Protective Action Criteria (PAC) TEEL-0: 11.8 mg/m3
2218
Potassium ferrocyanide
PAC-1: 35.4 mg/m3 PAC-2: 59 mg/m3 PAC-3: 59 mg/m3 OSHA PEL: 5 mg[CN]/m3/4.7 ppm TWA. NIOSH REL: 5 mg[CN]/m3/4.7 ppm/10 min Ceiling Concentration. ACGIH TLV®[1]: 5 mg[CN]/m3 [skin] Ceiling Concentration. DFG MAK: 2 mg[CN]/m3 , inhalable fraction TWA; Peak Limitation Category II(1) [skin]; Pregnancy Risk Group: C. NIOSH IDLH: 25 mg[CN]/m3. Determination in Air: Use NIOSH Analytical Method #7904, Cyanides. Permissible Concentration in Water: As of 1980, the criteria are: To protect freshwater aquatic life: 3.5 μg/L as a 24h average, never to exceed 52.0 μg/L. To protect saltwater aquatic life: 30.0 μg/L on an acute toxicity basis; 2.0 μg/L on a chronic toxicity basis. To protect human health: 200 μg/L. The allowable daily intake for man is 8.4 mg/ day.[6] On the international scene, the South African Bureau of Standards has set 10 μg/L, the World Health Organization (WHO) 10 μg/L and Germany 50 μg/L as drinking water standards. Other international limits[35] include an EEC limit of 50 μg/L; Mexican limits of 200 μg/L in drinking water and 1.0 μg/L in coastal waters and a Swedish limit of 100 μg/L. Russia[43] set a MAC of 100 μg/L in water bodies used for domestic purposes and 50 μg/L in water for fishery purposes. The US EPA[49] has determined a no-observed-adverse-effect-level (NOAEL) of 10.8 mg/kg/day which yields a lifetime health advisory of 154 μg/L. States which have set guidelines for cyanides in drinking water[61] include Arizona at 160 μg/L and Kansas at 220 μg/L. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Insufficient data are available on the effect of this substance on human health. However, this is a cyanide compound; therefore, utmost care must be taken. May cause eye irritation. May be harmful if swallowed. Animal studies suggest that the lethal dose is 48 oz for an adult. Long Term Exposure: No information available. Medical Surveillance: There is no special test for this chemical. However, if illness occurs or overexposure is suspected, medical attention is recommended. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical
facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Use amyl nitrate capsules if symptoms of cyanide poisoning develop. All area employees should be trained regularly in emergency measures for cyanide poisoning and in CPR. A cyanide antidote kit should be kept in the immediate work area and must be rapidly available. Kit ingredients should be replaced every 12 years to ensure freshness. Persons trained in the use of this kit, oxygen use, and CPR must be quickly available. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved half-face, dust/mist respirator. For emergencies or instances where the exposure levels are not known, use a full-face positive-pressure, airsupplied respirator operated in the positive-pressure mode, or use a NIOSH/MSHA- or European Standard EN149approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positivepressure mode. Note: Air-purifying respirators do not protect workers in oxygen-deficient atmospheres. Storage: Color Code—Green: General storage may be used. Prior to working with this chemical you should be trained on its proper handling and storage. Store away from incompatible materials listed above. Where possible, automatically transfer material from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of this chemical should be grounded and bonded. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: Not regulated. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially
Potassium fluoride contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Poisonous gases are produced in fire. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosionproof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Reference New York State Department of Health. (February 1986). Chemical Fact Sheet: Potassium Ferrocyanide. Albany, NY: Bureau of Toxic Substance Assessment
Potassium fluoride
P:0940
Molecular Formula: FK Common Formula: KF Synonyms: Fluorure de potassium (French); Potassium fluorure (French) CAS Registry Number: 7789-23-3 RTECS® Number: TT0700000 UN/NA & ERG Number: UN1812/154 EC Number: 232-151-5 [Annex I Index No.: 009-005-00-2] Regulatory Authority and Advisory Bodies Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. European/International Regulations: Hazard Symbol: T; Risk phrases: R23/24/25; Safety phrases: S1/2; S26; S45 (see Appendix 4). WGK (German Aquatic Hazard Class): 1—Low hazard to waters. Description: Potassium fluoride is a white crystalline solid. Molecular weight 5 58.10; Boiling point 5 1505 C; Freezing/Melting point 5 860 C. Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 0, Reactivity 0. Soluble in water. Potential Exposure: Potassium fluoride is used in etching glass, as a preservative, and as an insecticide. Incompatibilities: Strong acids. Permissible Exposure Limits in Air OSHA PEL: 3 ppm/2.5 mg[F]/m3 TWA. NIOSH REL: 3 ppm/2.5 mg[F]/m3 TWA; 6 ppm/5 mg[F]/m3, 15 min Ceiling Concentration.
2219
ACGIH TLV®[1]: 2.5 mg[F]/m3 TWA; not classifiable as a human carcinogen; BEI: 3 mg[F]/g creatinine in urine prior to end-of-shift; 10 mg[F]/g creatinine in urine end-of-shift. Protective Action Criteria (PAC) TEEL-0: 7.65 mg/m3 PAC-1: 7.65 mg/m3 PAC-2: 30 mg/m3 PAC-3: 500 mg/m3 DFG MAK: 1 mg[F]/m3, inhalable fraction [skin]; Peak Limitation Category II(4); Pregnancy Risk Group C; BAT: 7.0 mg[F]/g creatinine in urine at end-of-shift; 4.0 mg[F]/g creatinine in urine at the beginning of the next shift. NIOSH IDLH: 250 mg[F]/m3. Russia[43] has set a MAC value of 0.03 mg/m3 for soluble fluorides in ambient air in residential areas on a momentary basis and 0.01 mg/m3 on a daily average basis. Several states have set limits for fluoride in ambient air[60] ranging from as low as 2.85 μg/m3 (Iowa) to as high as 60,000 μg/ m3 (Kentucky). The reader is referred to the entry on “Fluorides” for more detail. Permissible Concentration in Water: Fluoride is a safe drinking water act-regulated chemical (47FR9352, 56FR 3594); MCL 5 4.0 mg/L; MCLG 5 4.0 mg/L; SMCL 5 2.0 mg/L. The state of Maine has set 2.4 mg/L as a guideline for drinking water. Arizona[61] has set 1.8 mg/L as a standard for drinking water. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Potassium fluoride can affect you when breathed in. Inhalation of dust or mist can cause severe irritation and burns of the eyes and skin. May cause permanent eye damage. Inhalation can cause irritation of the nose and throat causing sneezing, coughing, and sore throat. High exposure can irritate the lungs, causing a buildup of fluid in the lungs. This can cause death. Long Term Exposure: These effects do not occur at the levels of fluorides used in water to prevent cavities. Repeated exposure can cause fluoride to buildup in the body. Can irritate the lungs; bronchitis may develop. Repeated exposure can cause fluoride to build up in the body causing stiffness, brittle bones, and crippling. Prolonged contact can cause sores in the nose and perforated septum. Points of Attack: Lungs, skin. Medical Surveillance: NIOSH lists the following tests: chest X-ray, electrocardiogram, pulmonary function tests: forced vital capacity, forced expiratory volume (1 s); pelvic X-ray; sputum cytology; urine (chemical/metabolite); urine (chemical/metabolite) pre- and postshift; urinalysis (routine); complete blood count/differential. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 30 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately
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Potassium fluoride
with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. If victim is conscious, administer water or milk. Do not induce vomiting. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: NIOSH/OSHA 12.5 mg/m3: Qm (APF 5 25) (any quarter-mask respirator). 25 mg/m3: 95XQ (APF 5 10)* [any particulate respirator equipped with an N95, R95, or P95 filter (including N95, R95, and P95 filtering face-pieces) except quarter-mask respirators. The following filters may also be used: N99, R99, P99, N100, R100, P100] or SA* (any supplied-air respirator). 62.5 mg/ m3: Sa:Cf (APF 5 25)*† (any supplied-air respirator operated in a continuous-flow mode) or PaprHie (APF 5 25)* if not present as a fume (any powered, air-purifying respirator with a high-efficiency particulate filter). 125 mg/m3: 100F (APF 5 50)† [any particulate respirator equipped with an N95, R95, or P95 filter (including N95, R95, and P95 filtering face-pieces) except quarter-mask respirators. The following filters may also be used: N99, R99, P99, N100, R100, P100] or SCBAF (APF 5 50) (any self-contained breathing apparatus with a full face-piece) or SaF (APF 5 50) (any supplied-air respirator with a full facepiece). 250 mg/m3: Sa: Pd,Pp (APF 5 1000) (any suppliedair respirator operated in a pressure-demand or other positive-pressure mode). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd, Pp (APF 5 10,000) (any self-contained breathing apparatus that has a full faceplate and is operated in a pressuredemand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary, self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: 100F (APF 5 50)† [any particulate respirator equipped with an N95, R95, or P95 filter (including N95, R95, and P95 filtering face-pieces) except quarter-mask respirators. The
following filters may also be used: N99, R99, P99, N100, R100, P100] or SCBAE (any appropriate escape-type, selfcontained breathing apparatus). *Substance reported to cause eye irritation or damage; may require eye protection. † May need acid gas sorbent. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Potassium fluoride must be stored to avoid contact with strong acids (such as hydrochloric, sulfuric, and nitric) since violent reactions occur. Where possible, automatically transfer material from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of this chemical should be grounded and bonded. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: This compound requires a shipping label of “POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 6.1 and Packing Group III. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: Use dry chemical, carbon dioxide, water spray, or foam extinguishers. Poisonous gases are produced in fire, including potassium oxide and fluorine. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Reference New Jersey Department of Health and Senior Services. (November 2004). Hazardous Substances Fact Sheet: Potassium Fluoride. Trenton, NJ
Potassium hydroxide
Potassium hydroxide
P:0950
Molecular Formula: HKO Common Formula: KOH Synonyms: Caustic potash; Hidroxido potasico (Spanish); Hydroxide de potassium (French); Kaliumhydroxid (German); KOH; LYE; Potassa; Potasse caustique (French); Potassium hydrate; Potassium (hydrixyde de) (French) CAS Registry Number: 1310-58-3 RTECS® Number: TT2100000 UN/NA & ERG Number: UN1813 (solid)/154; UN1814 (solution)/154 EC Number: 215-181-3 [Annex I Index No.: 019-002-00-8] Regulatory Authority and Advisory Bodies Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. US EPA, FIFRA 1998 Status of Pesticides: Canceled. Clean Water Act: Section 311 Hazardous Substances/RQ 40CFR117.3 (same as CERCLA, see below). Reportable Quantity (RQ): 1000 lb (454 kg). Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: not listed in Annex 1. WGK (German Aquatic Hazard Class): 1—Low hazard to waters. Description: Potassium hydroxide is a white deliquescent solid. Molecular weight 5 56.11; Specific gravity (H2O:1) 5 2.04 at 25 C; Boiling point 5 1324 C; Freezing/Melting point 5 380 C; also reported at 405 C (varies with water content). Hazard Identification (based on NFPA-704 M Rating System) (45%): Health 3, Flammability 0, Reactivity 1. Soluble in water; solubility 5 107% at 15 C; reaction. Potential Exposure: Compound Description: Agricultural Chemical; Mutagen, Primary Irritant. Used in the manufacture of other potassium compounds and in the general use of KOH as an alkali. Incompatibilities: A strong base. Violent reaction with acids, water, metals (when wet), halogenated hydrocarbons, maleic anhydride. Heat is generated if KOH comes in contact with water and carbon dioxide from the air. Corrosive to zinc, aluminum, tin, and lead in the presence of moisture, forming a combustible/explosive hydrogen gas. Can absorb water from air and give off sufficient heat to ignite surrounding combustible materials. Permissible Exposure Limits in Air OSHA PEL: None. NIOSH REL: 2 mg/m3 Ceiling Concentration. ACGIH TLV®[1]: 2 mg/m3 Ceiling Concentration. Protective Action Criteria (PAC) TEEL-0: 0.1 mg/m3 PAC-1: 0.3 mg/m3 PAC-2: 2 mg/m3 PAC-3: 125 mg/m3 Australia: TWA 2 mg/m3, 1993; Austria: MAK 2 mg/m3, 1999; Belgium: STEL 2 mg/m3, 1993; Denmark: TWA
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2 mg/m3, 1999; Finland: TWA 2 mg/m3, 1999; Japan: STEL 2 mg/m3, 1999; Norway: TWA 2 mg/m3, 1999; the Netherlands: MAC 2 mg/m3, 2003; Switzerland: MAK-W 2 mg/m3, 1999; United Kingdom: STEL 2 mg/m3, 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: Ceiling Concentration 2 mg/m3. Several states have set guidelines or standards for KOH in ambient air[60] ranging from 16.0 μg/m3 (Virginia) to 20 μg/m3 (North Dakota) to 48 μg/ m3 (Nevada). Determination in Air: Use NIOSH Analytical Method (IV) #7401, alkaline Dusts. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Potassium hydroxide can affect you when breathed in. Potassium hydroxide is highly corrosive. Eye contact causes immediate severe burns and can lead to blindness. Skin contact causes severe skin burns. Exposure can irritate the nose, throat, and airways, causing sneezing, coughing, and sores in the nose. Higher levels can irritate the lungs and cause a buildup of fluid (pulmonary edema). This can cause death. Ingestion may be fatal; causes epigastrium, hermatemesis, collapse, and stricture of esophagus. Long Term Exposure: May cause sores in the nose and perforation of the nasal septum. May cause lung damage. Points of Attack: Eyes, skin, respiratory system. Medical Surveillance: Before beginning employment and at regular times after that, for those with frequent or potentially high exposures, the following is recommended: lung function tests. If symptoms develop or overexposure is suspected, the following may be useful: consider chest X-ray after acute overexposure. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 45 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. If victim is conscious, administer water or milk. Do not induce vomiting. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. For solutions of 3070%,
2222
Potassium nitrate
natural rubber; Neoprene™, nitrile, nitrile 1 PVC, Neoprene™ 1 natural rubber, and polyethylene are recommended. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield when working with liquid, or wear dustproof goggles and face shield when working with powders or dusts unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Where there is potential for exposures over 2 mg/m3, use a NIOSH/MSHA- or European Standard EN 149-approved full-face-piece respirator with a high-efficiency particulate filter. More protection is provided by a powered air-purifying respirator. Particulate filters must be checked every day before work for physical damage, such as rips or tears, and replaced as needed. Where there is potential for high exposures, use a NIOSH/MSHA- or European Standard EN 149-approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuous-flow mode; or use a NIOSH/MSHA- or European Standard EN 149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—White Stripe: Contact Hazard; Store separately; not compatible with materials in solid white category. Prior to working with this chemical you should be trained on its proper handling and storage. Potassium hydroxide must be stored to avoid contact with water or moisture and metals since violent reactions occur. Store in tightly closed containers in a cool, well-ventilated area away from acids, explosives, combustible materials, and organic peroxides. Where possible, automatically pump liquid from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Shipping: Potassium hydroxide, solid or solution, requires a shipping label of “CORROSIVE.” The solid falls in DOT Hazard Class 8 and Packing Group II. The solution falls in DOT Hazard Class 8 and Packing Group II or III. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Ventilate the area of spill or leak. Absorb liquids in vermiculite, dry sand, earth, or a similar material and deposit in sealed containers. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are
required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: Potassium hydroxide may ignite surrounding material if it absorbs water. Extinguish fire using an agent suitable for type of surrounding fire. Potassium hydroxide itself does not burn. Poisonous gases are produced in fire, including potassium oxide. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Dilute with large volume of water, neutralize and flush to sewer.[22] Reference New Jersey Department of Health and Senior Services. (May 2001). Hazardous Substances Fact Sheet: Potassium Hydroxide. Trenton, NJ
Potassium nitrate
P:0960
Molecular Formula: KNO3 Synonyms: Kaliumnitrat (German); Niter; Nitre; Nitric acid, potassium salt; Saltpeter; Vicknite CAS Registry Number: 7757-79-1 RTECS® Number: TT3700000 UN/NA & ERG Number: UN1486/140 EC Number: 231-818-8 Regulatory Authority and Advisory Bodies Department of Homeland Security Screening Threshold Quantity (pounds): Theft hazard 400 (Commercial grade). US EPA, FIFRA 1998 Status of Pesticides: RED completed. FDA—over-the-counter drug. Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. WGK (German Aquatic Hazard Class): 1—Low hazard to waters. Description: Potassium nitrate is an odorless, white or colorless crystalline powder with a salty taste. Molecular weight 5 179.31; Boiling point 5 (decomposes) 400 C; Freezing/Melting point 5 334 C. Hazard Identification (based on NFPA-704 M Rating System): Health 2, Flammability 0, Reactivity 3 (Oxidizer). Highly soluble in water; solubility 5 36% at 25 C. Potential Exposure: Compound Description: Drug, Mutagen; Reproductive Effector. Used to make explosives,
Potassium nitrate gunpowder, fireworks, rocket fuel, matches, fertilizer, fluxes, glass manufacture; and as a diuretic. Incompatibilities: A powerful oxidizer. Dangerously reactive and friction- and shock-sensitive when mixed with organic materials and many materials. Violent reactions with reducing agents, chemically active metals, charcoal, trichloroethylene. Permissible Exposure Limits in Air Protective Action Criteria (PAC) TEEL-0: 0.4 mg/m3 PAC-1: 1.25 mg/m3 PAC-2: 7.5 mg/m3 PAC-3: 500 mg/m3 Russia: STEL 5 mg/m3, 1993. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Contact can cause eye and skin irritation. Inhalation can cause respiratory tract irritation, coughing, and wheezing. High levels of exposure can interfere with the blood’s ability to carry oxygen, causing headache, dizziness, cyanosis, methemoglobinemia, with blue color to the skin and lips. Higher levels can cause breathing difficulty, collapse, and death. Long Term Exposure: There is limited evidence that this chemical can damage the developing fetus. Points of Attack: Blood. Medical Surveillance: Blood test for methemoglobin. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Note to physician: Treat for methemoglobinemia. Spectrophotometry may be required for precise determination of levels of methemoglobin in urine. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash.
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Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—Yellow: Reactive Hazard; Store in a location separate from other materials, especially flammables and combustibles. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, wellventilated area away from all other materials. Do not store on wooden floors. Where possible, automatically transfer material from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of this chemical should be grounded and bonded. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. See OSHA Standard 1910.104 and NFPA 43A Code for the Storage of Liquid and Solid Oxidizers for detailed handling and storage regulations. See also 29 CFR 1910.101 for specific regulations on storage of compressed gas cylinders. Shipping: Potassium nitrate requires a shipping label of “OXIDIZER.” It falls in Hazard Class 5.1 and Packing Group III. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible solid. Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Poisonous gases are produced in fire. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and
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Potassium nitrite
equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Reference New Jersey Department of Health and Senior Services. (November 2004). Hazardous Substances Fact Sheet: Potassium Nitrate. Trenton, NJ
Potassium nitrite
P:0970
Molecular Formula: KNO2 Synonyms: Kaliumnitrat (German); Niter; Nitre; Nitrous acid, Potassium salt; Saltpeter; Vicknite CAS Registry Number: 7758-09-0 RTECS® Number: TT3750000 UN/NA & ERG Number: UN1488/140 EC Number: 231-832-4 [Annex I Index No.: 007-011-00-X] Regulatory Authority and Advisory Bodies Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Canada, WHMIS, Ingredients Disclosure List Concentration 0.1%. European/International Regulations: Hazard Symbol: C; Risk phrases: R22; R35; Safety phrases: S1/2; S26; S36/37/ 39; S45 (see Appendix 4). WGK (German Aquatic Hazard Class): 2—Hazard to waters. Description: Potassium nitrite is a white to yellowish crystalline solid. Molecular weight 5 85.11; Boiling point 5 decomposition starts at 350 C; explosion at 535 C; Freezing/Melting point 5 441 C. Hazard Identification (based on NFPA-704 M Rating System): Health 0, Flammability 1, Reactivity 2 (Oxidizer). Soluble in water; solubility 5 280 g/100 mL. Potential Exposure: Compound Description: Drug, Mutagen; Reproductive Effector; Human Data. Potassium nitrite is used in chemical analysis, as a food additive; in fertilizers; in medications as a vasodilator and as antidote for cyanide poisoning. Incompatibilities: A strong oxidizer. Reacts violently with combustible and reducing materials. Heat above 530 C may cause explosion. Incompatible with cyanide salts; boron, ammonium sulfate, potassium amide, and acids. Decomposes on contact with even weak acids, producing toxic nitrogen oxide fumes. Permissible Exposure Limits in Air Protective Action Criteria (PAC) TEEL-0: 0.04 mg/m3 PAC-1: 0.1 mg/m3 PAC-2: 0.75 mg/m3 PAC-3: 500 mg/m3 Routes of Entry: Inhalation, ingestion, skin and/or eye contact.
Harmful Effects and Symptoms Short Term Exposure: Potassium nitrite can affect you when breathed in. Contact can cause eye and skin burns. Breathing the dust or mist can irritate the nose, throat, and lungs, and may cause cough with phlegm. Higher exposures can cause pulmonary edema, a medical emergency that can be delayed for several hours. This can cause death. High levels can affect the vascular system and interfere with the ability of the blood to carry oxygen (methemoglobinemia), causing headaches, weakness, dizziness, and cyanosis, a bluish color to the skin and lips. Higher levels can cause troubled breathing, collapse, and even death. Long Term Exposure: Repeated skin contact causes dermatitis, drying, and cracking. May cause lung irritation; bronchitis may develop. There is limited evidence that potassium nitrite may damage the developing fetus. Points of Attack: Eyes, skin, blood, lungs. Medical Surveillance: If symptoms develop or overexposure is suspected, the following may be useful: blood test for methemoglobin. Lung function tests. Consider chest X-ray after acute overexposure. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. Note to physician: Treat for methemoglobinemia. Spectrophotometry may be required for precise determination of levels of methemoglobin in urine. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Where there is potential for exposure to potassium nitrite, use a NIOSH/MSHA- or European
Potassium permanganate Standard EN149-approved full-face-piece respirator with a high-efficiency particulate filter. Greater protection is provided by a powered air-purifying respirator. Where there is potential for high exposures, use a NIOSH/MSHA- or European Standard EN149-approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuous-flow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—Yellow: Reactive Hazard; Store in a location separate from other materials, especially flammables and combustibles. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, wellventilated area away from acids, cyanide salts, boron, ammonium sulfate, and potassium amide. Where possible, automatically transfer material from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of this chemical should be grounded and bonded. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. See OSHA Standard 1910.104 and NFPA 43A Code for the Storage of Liquid and Solid Oxidizers for detailed handling and storage regulations. Shipping: Potassium nitrite requires a shipping label of “OXIDIZER.” It falls in Hazard Class 5.1 and Packing Group II. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. Keep potassium nitrite out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: Does not burn but may ignite other combustible materials. Use dry chemical, CO2, water spray, or foam extinguishers. Poisonous gases are produced in fire, including oxides of nitrogen. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound
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increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Reference New Jersey Department of Health and Senior Services. (November 2004). Hazardous Substances Fact Sheet: Potassium Nitrite. Trenton, NJ
Potassium permanganate
P:0980
Molecular Formula: KMnO4 Synonyms: Cairox; Chameleon mineral; C.I. 77755; Condy’s crystals; Kaliumpermanganat (German); Permanganic acid, potassium salt; Permanganate de potassium (French); Permanganate of potash; Permanganato potasico (Spanish); Potassium (permanganate de) (French); Purple salt CAS Registry Number: 7722-64-7 RTECS® Number: SD6475000 UN/NA & ERG Number: UN1490/140 EC Number: 231-760-3 [Annex I Index No.: 025-002-00-9] Regulatory Authority and Advisory Bodies Department of Homeland Security Screening Threshold Quantity (pounds): Theft hazard 400 (Commercial grade). US EPA Gene-Tox Program, Negative: In vitro cytogenetics—nonhuman; N. crassa—reversion; Negative: B. subtilis rec assay. US EPA, FIFRA 1998 Status of Pesticides: Pesticide subject to registration or re-registration. Clean Water Act: Section 311 Hazardous Substances/RQ 40CFR117.3 (same as CERCLA, see below). Reportable Quantity (RQ): 100 lb (45.4 kg). European/International Regulations: Hazard Symbol: O, Xn, N; Risk phrases: R8; R22; R36/37/38; R42/43; Safety phrases: S2; S22; S24; S26; S37 (see Appendix 4). WGK (German Aquatic Hazard Class): 3—Severe hazard to waters. Description: Potassium permanganate is a dark purple crystalline solid. Molecular weight 5 158.04; Freezing/Melting point 5 (decomposition, with evolution of oxygen) ,240 C. Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 0, Reactivity 3 (Oxidizer). Highly soluble in water. Potential Exposure: Compound Description: Agricultural Chemical; Mutagen; Reproductive Effector; Human Data. Potassium permanganate is used in solutions as a disinfectant, topical antibacterial agent; deodorizer, bleaching agent; and in air and water purification. Incompatibilities: Potassium permanganate is a powerful oxidizing agent, that is, it will initiate a fire or explosion if
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Potassium permanganate
brought into contact with reducing materials, combustibles, organic materials; strong acids; or oxidizable solid, liquid, or gas; glycerine, ethylene glycol, polypropylene, hydroxylamine, hydrogen trisulfide, antimony, arsenic, sulfuric acid, hydrogen peroxide, phosphorus, and any finely divided combustible material. It will decompose, and release oxygen if brought into contact with heat, alcohol, acids, ferrous salts, iodides and oxalates. Permissible Exposure Limits in Air OSHA PEL: 5 mg[Mn]/m3 Ceiling Concentration. NIOSH: 1 mg[Mn]/m3 TWA; 3 mg[Mn]/m3 STEL. ACGIH TLV®[1]: TWA 0.2 mg[Mn]/m3, inorganic compounds. NIOSH IDLH: 500 mg[Mn]/m3. Protective Action Criteria (PAC) TEEL-0: 0.575 mg/m3 PAC-1: 8.63 mg/m3 PAC-2: 14.4 mg/m3 PAC-3: 500 mg/m3 DFG MAK: 0.5 mg[Mn]/m3 inhalable fraction (Mn and its inorganic compounds); Pregnancy Risk Group C. Australia: TWA 5 mg[Mn]/m3, 1993; Belgium: TWA 5 mg [Mn]/m3, 1993; Denmark: TWA 2.5 mg[Mn]/m3, 1999; Finland: TWA 0.5 mg[Mn]/m3, 1999; Hungary: TWA 0.3 mg[Mn]/m3, short-term exposure limit 0.6 mg[Mn]/m3, 1993; Japan: 0.3 mg[Mn]/m3, respirable dust, 1999; Poland: MAC (TWA) 0.3 mg[Mn]/m3; MAC 5 mg[Mn]/m3, 1999; Sweden: NGV 1 mg[Mn]/m3, KTV 2.5 mg[Mn]/m3 (respirable dust), 1999; Sweden: NGV 2.5 mg[Mn]/m3, KTV 5 mg[Mn]/m3 (total dust), 1999; United Kingdom: LTEL 5 mg[Mn]/m3, 1993; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: TWA 0.2 mg[Mn]/m3. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Inhalation: Irritates the respiratory tract, causing coughing and chest tightness. Higher exposures can cause pulmonary edema, a medical emergency that can be delayed for several hours. This can cause death. Skin: Concentrated solutions may cause severe irritation and burns. Dilute solutions can cause brown staining of the skin and hardening of outer skin layer. Penetration is poor. Eyes: Concentrated solution or crystalline material can cause severe irritation and damage that may be permanent. Ingestion: Dilute solutions (1%) may cause burning of the throat, nausea, vomiting, and stomach pain. Concentrations of 23% may cause anemia and swelling of the throat with a possibility of suffocation. More concentrated solutions may result in above symptoms plus the onset of kidney damage and circulatory collapse. The probable lethal dose is 11/2 teaspoons (10 g) for a 150-lb (70 kg) adult. Long Term Exposure: May cause mutations and might pose a cancer risk or reproduction hazard. May cause lung effects. Points of Attack: Lungs, skin.
Medical Surveillance: NIOSH lists the following tests (for manganese and fume): whole blood (chemical/metabolite); biologic tissue/biopsy; Complete blood count; chest X-ray; pulmonary function tests; urine (chemical/metabolite); urinalysis (routine). For those with frequent or potentially high exposure the following are recommended before beginning work and at regular times after that: lung function tests. If symptoms develop or overexposure is suspected, the following may be useful: consider chest X-ray after acute overexposure. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give egg whites and milk. A tracheotomy may be required if swelling in throat blocks air. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield when working with liquid unless full face-piece respiratory protection is worn. Wear dust-proof goggles when working with powders or dust unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Up to 10 mg/m3: 95XQ (APF 5 10) [any particulate respirator equipped with an N95, R95, or P95 filter (including N95, R95, and P95 filtering facepieces) except quarter-mask respirators. The following filters may also be used: N99, R99, P99, N100, R100, P100] or Sa (APF 5 10) (any supplied-air respirator). Up to 25 mg/m3: Sa:Cf (APF 5 25) (any supplied-air respirator operated in a continuous-flow mode); PaprHie (APF 5 25) (any powered air-purifying respirator with a high-efficiency particulate filter). Up to 50 mg/m3: 100F (APF 5 50) (any air-purifying, full-face-piece respirator with an N100, R100, or P100 filter) or SaT: Cf (APF 5 50) (any supplied-air respirator that has a tight-fitting face-piece and is operated in a continuous-flow mode) or PaprTHie (APF 5 50) (any
Potassium persulfate powered, air-purifying respirator with a tight-fitting facepiece and a high-efficiency particulate filter) or SCBAF (APF 5 50) (any self-contained breathing apparatus with a full face-piece) or SaF (APF 5 50) (any supplied-air respirator with a full face-piece). Up to 500 mg/m3: Sa: Pd,Pp (APF 5 1000) (any supplied-air respirator operated in a pressure-demand or other positive-pressure mode). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd,Pp (APF 5 10,000) (any self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode); ASCBA (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary self-contained positive-pressure breathing apparatus). Escape: 100F (APF 5 50) (any air-purifying, full-face-piece respirator with an N100, R100, or P100 filter) or SCBAE (any appropriate escape-type, self-contained breathing apparatus). Storage: Color Code—Yellow: Reactive Hazard; Store in a location separate from other materials, especially flammables and combustibles. Prior to working with this chemical you should be trained on its proper handling and storage. Potassium permanganate must be stored to avoid contact with strong acids (such as hydrochloric, sulfuric, and nitric), any organic material, or any other combustible or oxidizable solid, liquid, or gas since violent reactions occur. Store in tightly closed containers in a cool, wellventilated area. Protect containers from physical damage. Where possible, automatically transfer material from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of this chemical should be grounded and bonded. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. See OSHA Standard 1910.104 and NFPA 43A Code for the Storage of Liquid and Solid Oxidizers for detailed handling and storage regulations. Shipping: Potassium permanganate requires a shipping label of “OXIDIZER.” It falls in Hazard Class 5.1 and Packing Group II. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Liquid: Ventilate area of spill or leak. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Dry material: Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. Large spills: Clean up should be performed by trained personnel. Cover the weak reducing agents, such as sodium thiosulfate, bisulfites, or ferrous salts. Bisulfites or ferrous salts need an additional promoter of three molar sulfuric acids to accelerate reaction. Transfer slurry or sludge to large container of water and neutralize with soda ash. Keep potassium
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permanganate out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: Potassium permanganate does not burn. However, it is a powerful oxidizer. Potassium permanganate decomposes at 240 C/464 F and releases oxygen which will greatly intensify an ongoing fire. Use dry chemical or carbon dioxide extinguishers. Poisonous gases are produced in fire, including potassium oxide. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: React with reducing agent, neutralize and flush to sewer.[22] References Sax, N. I. (Ed.). (1988). Dangerous Properties of Industrial Materials Report, 8, No. 4, 212 New Jersey Department of Health and Senior Services. (February 1986). Hazardous Substances Fact Sheet: Potassium Permanganate. Version 2 and 3. Albany, NY: Bureau of Toxic Substance Assessment New Jersey Department of Health and Senior Services. (May 2002). Hazardous Substances Fact Sheet: Potassium Permanganate. Trenton, NJ
Potassium persulfate
P:0990
Molecular Formula: K2O8S2 Common Formula: K2S2O8 Synonyms: Anthion; Dipotassium peroxodisulphate; Dipotassium persulfate; Potassium persulphate; Potassium peroxydisulphate; Potassium peroxydisulfate; Peroxydisulfuric acid, Disodium salt CAS Registry Number: 7727-21-1 RTECS® Number: SE0400000 UN/NA & ERG Number: UN1492/140
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Potassium persulfate
EC Number: 231-781-8 [Annex I Index No.: 016-061-00-1] [dipotassium peroxodisulphate] Regulatory Authority and Advisory Bodies European/International Regulations: Hazard Symbol: O, Xn; Risk phrases: R8; R22; R36/37/38; R42/43; Safety phrases: S2; S22; S24; S26; S37 (see Appendix 4). WGK (German Aquatic Hazard Class): 1—Low hazard to waters. Description: Potassium persulfate is a colorless or white, odorless crystalline material. Molecular weight 5 272.34; Boiling point 5 109.5 C; Freezing/Melting point 5 (decomposes) ,100 C. Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 0, Reactivity 3. Oxidizer. Soluble in water. Potential Exposure: Potassium persulfate is used as a bleaching and oxidizing agent; it is used in redox polymerization catalysts; in the defiberizing of wet strength paper and in the desizing of textiles. Soluble in water. Incompatibilities: A strong oxidizer. Combustible, organic or other readily oxidizable materials, sulfur, metallic dusts, such as aluminum dust, chlorates, and perchlorates. Attacks chemically active metals. Keep away from moisture. Permissible Exposure Limits in Air ACGIH: 0.1 mg [S2O8]/m3 TWA as persulfates. Protective Action Criteria (PAC) TEEL-0: 0.1 mg/m3 PAC-1: 10 mg/m3 PAC-2: 60 mg/m3 PAC-3: 350 mg/m3 Permissible Concentration in Water: No criteria set. (Aqueous solution decomposes even at room temperature). Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Potassium persulfate can affect you when breathed in. Breathing the dust or mist can cause eye, nose, and throat irritation with sneezing, coughing, and sore throat. Contact with skin and eyes can cause burns and permanent damage. Prolonged or repeated exposures may lead to sores of the inner nose. Higher exposures can cause pulmonary edema, a medical emergency that can be delayed for several hours. This can cause death. Long Term Exposure: May cause sores of the inner nose. Skin contact may cause skin rash, with dryness and cracking. May cause lung irritation. Points of Attack: Lungs. Medical Surveillance: For those with frequent or potentially high exposure the following are recommended before beginning work and at regular times after that: lung function tests. If symptoms develop or overexposure is suspected, the following may also be useful: consider chest X-ray after acute overexposure. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the
skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Use a NIOSH/MSHA- or European Standard EN 149-approved dust mask when dust is encountered. Where there is potential for exposures over 5 mg/m3, use a NIOSH/MSHA- or European Standard EN149approved full-face-piece respirator with a high-efficiency particulate filter. Greater protection is provided by a powered air-purifying respirator. Where there is potential for high exposures, use a NIOSH/MSHA- or European Standard EN149-approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuous-flow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—Yellow: Reactive Hazard; Store in a location separate from other materials, especially flammables and combustibles. Prior to working with this chemical you should be trained on its proper handling and storage. Potassium persulfate must be stored to avoid contact with oxidizers (such as perchlorates, peroxides, permanganates, chlorates, and nitrates), strong oxidizers (such as chlorine, bromine, and fluorine), and chemically active metals (such as potassium, sodium, magnesium, and zinc) since violent reactions occur. Protect storage against physical damage. Store in tightly closed containers in a cool, well-ventilated area away from moisture. See OSHA Standard 1910.104 and NFPA 43A Code for the Storage of Liquid and Solid Oxidizers for detailed handling and storage regulations.
Potassium silver cyanide Shipping: Potassium persulfate requires a shipping label of “OXIDIZER.” It falls in Hazard Class 5.1 and Packing Group III. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. Keep potassium persulfate out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible solid. Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Poisonous gases are produced in fire, including oxides of sulfur. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Use large volumes of reducing agents (e.g., bisulfites). Neutralize with soda ash and drain into sewer with abundant water. Reference New Jersey Department of Health and Senior Services. (May 1986). Hazardous Substances Fact Sheet: Potassium Persulfate. Trenton, NJ
Potassium silver cyanide
P:1000
Molecular Formula: AgC2KN2 Common Formula: KAg(CN)2 Synonyms: Cianuro de plata y potasio (Spanish); Dicyano potassium argentate; Potassium dicyanoargentate; Silver potassium cyanide CAS Registry Number: 506-61-6 RTECS® Number: TT5775000 UN/NA & ERG Number: UN1588/157 EC Number: 208-047-0 (potassium dicyanoargentate)
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Regulatory Authority and Advisory Bodies US EPA Hazardous Waste Number (RCRA No.): P099. RCRA, 40CFR261, Appendix 8 Hazardous Constituents. Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 500 lb (227 kg). Reportable Quantity (RQ): 1 lb (0.454 kg). Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. Cyanide compounds: Clean Air Act: Hazardous Air Pollutants (Title I, Part A, Section 112). Clean Water Act: 40CFR423, Appendix A, Priority Pollutants, as cyanide, total. US EPA Hazardous Waste Number (RCRA No.): P030 as cyanides soluble salts and complexes, n.o.s. RCRA, 40CFR261, Appendix 8 Hazardous Constituents. as cyanides, soluble salts and complexes, n.o.s. EPCRA (Section 313): X 1 CN2 where X 5 H1 or any other group where a formal dissociation may occur. For example, KCN or Ca(CN)2. Form R de minimis concentration reporting level: 1.0%. Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%, Cyanide compounds, inorganic, n.o.s. US DOT Regulated Marine Pollutant (49CFR172.101, Appendix B) as cyanide mixtures, cyanide solutions or cyanides, inorganic, n.o.s. Silver compounds: Clean Water Act: Section 307 Toxic Pollutants as silver and compounds. RCRA Section 261 Hazardous Constituents, as silver compounds, n.o.s., waste number not listed. EPCRA (Section 313): Includes any unique chemical substance that contains silver as part of that chemical’s infrastructure. Form R de minimis concentration reporting level: 1.0%. WGK (German Aquatic Hazard Class): 3—Severe hazard to waters. Description: Potassium silver cyanide is a white crystalline solid. Molecular weight 5 199.01; Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 0, Reactivity 0. Soluble in water. Potential Exposure: Potassium silver cyanide is used in silver plating; as a bactericide; and in the manufacture of antiseptics. Not registered as a pesticide in the United States. Incompatibilities: Contact with acid, acid fumes, water, steam, or when heated to decomposition emits toxic and flammable cyanide vapors. May be light sensitive. Permissible Exposure Limits in Air OSHA PEL: 5 mg[CN]/m3/4.7 ppm TWA. NIOSH REL: 5 mg[CN]/m3/4.7 ppm/10 min Ceiling Concentration. ACGIH TLV®[1]: 5 mg[CN]/m3 [skin] Ceiling Concentration. NIOSH IDLH: 25 mg[CN]/m3. Protective Action Criteria (PAC) TEEL-0: 0.0184 mg/m3
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Potassium silver cyanide
PAC-1: 2.5 mg/m3 PAC-2: 18.4 mg/m3 PAC-3: 18.4 mg/m3 DFG MAK: 2 mg[CN]/m3, inhalable fraction TWA; Peak Limitation Category II(1) [skin]; Pregnancy Risk Group: C. Determination in Air: Use NIOSH Analytical Method (IV) #7904, Cyanides. See also Method #6010, Hydrogen cyanide.[18] Permissible Concentration in Water: In 1976 the EPA criterion was 5.0 μg/L for freshwater and marine aquatic life and wildlife. As of 1980, the criteria are: To protect freshwater aquatic life: 3.5 μg/L as a 24-h average, never to exceed 52.0 μg/L. To protect saltwater aquatic life: 30.0 μg/L on an acute toxicity basis; 2.0 μg/L on a chronic toxicity basis. To protect human health: 200 μg/L. The allowable daily intake for man is 8.4 mg/day.[6] On the international scene, the South African Bureau of Standards has set 10 μg/L, the World Health Organization (WHO) 10 μg/L, and Germany 50 μg/L as drinking water standards. Other international limits[35] include an EEC limit of 50 μg/L; Mexican limits of 200 μg/L in drinking water and 1.0 μg/L in coastal waters; and a Swedish limit of 100 μg/L. Russia[43] set a MAC of 100 μg/L in water bodies used for domestic purposes and 50 μg/L in water for fishery purposes. The US EPA[49] has determined a no-observed-adverseeffect-level (NOAEL) of 10.8 mg/kg/day which yields a lifetime health advisory of 154 μg/L. States which have set guidelines for cyanides in drinking water[61] include Arizona at 160 μg/L and Kansas at 220 μg/L. Determination in Water: Distillation followed by silver nitrate titration or colorimetric analysis using pyridine pyrazolone (or barbituric acid). Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Absorbed through the skin. Harmful Effects and Symptoms Short Term Exposure: The primary health hazard is as a cyanide. It is poisonous and may be fatal if inhaled, swallowed, or absorbed through the skin. Fire may produce irritating or poisonous gases. As a cyanide, massive doses may produce, without warning, sudden loss of consciousness and prompt death from respiratory arrest. Smaller but still lethal doses result in illness that may be prolonged for one or more hours. Other symptoms may include numbness in throat, salivation, nausea, anxiety, dizziness, irregular breathing, odor of bitter almonds may be noted on breath, blood pressure may rise, slowing of the heartbeat, sensation of constriction in the chest, unconsciousness followed by violent convulsions and paralysis. LD50 5 (oral-rat) 21 mg/kg. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If
this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Keep victim quiet and maintain normal body temperature. Effects may be delayed; keep victim under observation. Use amyl nitrate capsules if symptoms develop. All area employees should be trained regularly in emergency measures for cyanide poisoning and in CPR. A cyanide antidote kit should be kept in the immediate work area and must be rapidly available. Kit ingredients should be replaced every 12 years to ensure freshness. Persons trained in the use of this kit, oxygen use, and CPR must be quickly available. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Up to 25 mg/m3: Sa (APF 5 10) (any supplied-air respirator) or SCBAF (APF 5 50) (any selfcontained breathing apparatus with full face-piece). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd,Pp (APF 5 10,000) (any self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positivepressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: GmFS100 (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or back-mounted canister providing protection against the compound of concern and having an N100, R100, or P100 filter] or SCBAE (any appropriate escape-type, self-contained breathing apparatus). Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Shipping: Cyanides, inorganic, solid, n.o.s. require a shipping label of “POISONOUS/TOXIC MATERIALS.” They fall in Hazard Class 6.1. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered
Potassium sulfide material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: Use dry chemical, carbon dioxide, water spray, or foam for small fires; and water spray, fog, or foam for large fires. Move containers of this material away from fire area if this can be done without risk. Isolate hazard area and deny entry. Stay upwind; keep out of low areas. Ventilate closed spaces before entering them. Wear positive pressure breathing apparatus and special protective clothing. Fight fire from maximum distance. Dike fire control water for later disposal. Do not scatter the material. Poisonous gases are produced in fire. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant ($100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. Reference US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Potassium Silver Cyanide. Washington, DC: Chemical Emergency Preparedness Program
Potassium sulfide
P:1010
Molecular Formula: K2S Synonyms: Dipotassium monosulfide; Dipotassium sulfide; Hepar sulfurous; Potassium monosulfide CAS Registry Number: 1312-73-8 RTECS® Number: TT6000000 (anhydrous); TT6008000 (hydrated) UN/NA & ERG Number: UN1382 (anhydrous)/135; UN1847 (hydrated)/153 EC Number: 215-197-0 [Annex I Index No.: 016-006-00-1]
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Regulatory Authority and Advisory Bodies European/International Regulations: Hazard Symbol: C; Risk phrases: R31; R34; R50; Safety phrases: S1/2; S26; S45; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): 2—Hazard to waters. Description: Potassium sulfide is a brownish-red crystalline solid. Molecular weight 5 110.26; Freezing/Melting point 5 840 C. Soluble in water. Potential Exposure: Potassium sulfide is used as a reagent in analytical chemistry; and in pharmaceutical preparations. Incompatibilities: May explosively decompose from shock, friction, or concussion. May spontaneously ignite on contact with air. The aqueous solution is a strong base; reacts violently with strong acids and acid fumes. The solid material decomposes on contact with acids producing hydrogen sulfide, and oxidizers producing sulfur dioxide. Permissible Exposure Limits in Air No standards or TEEL available. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Potassium sulfide can affect you when breathed in. Breathing the dust or mist can irritate the eyes, nose, and throat with sneezing, coughing, and sore throat. Potassium sulfide is a corrosive chemical and contact with skin and eyes can cause burns. High exposures can cause pulmonary edema, a medical emergency that can be delayed for several hours. This can cause death. Long Term Exposure: Corrosive materials can cause lung problems; bronchitis may develop. Prolonged exposure can lead to sores or ulcers of the inner lining of the nose. Points of Attack: Lungs, skin. Medical Surveillance: Before beginning employment and at regular times after that, for those with frequent or potentially high exposures, the following are recommended: lung function tests. If symptoms develop or overexposure is suspected, the following may be useful: consider chest X-ray after acute overexposure. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. If victim is conscious, administer water or milk. Do not induce vomiting. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray.
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Procarbazine & procarbazine hydrochloride
Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Where there is potential for exposures to potassium sulfide use a NIOSH/MSHA- or European Standard EN149-approved full-face-piece respirator equipped with particulate (dust/fume/mist) filters. Particulate filters must be checked every day before work for physical damage, such as rips or tears, and replaced as needed. Where there is potential for high exposures and liquid potassium sulfide, use a NIOSH/MSHA- or European Standard EN149-approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuous-flow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—White: Corrosive or Contact Hazard; Store separately in a corrosion-resistant location. Prior to working with this chemical you should be trained on its proper handling and storage. Potassium sulfide must be stored to avoid contact with oxidizers (such as perchlorates, peroxides, permanganates, chlorates, and nitrates) and strong acids (such as hydrochloric, sulfuric, and nitric) since violent reactions occur. Sources of ignition, such as smoking and open flames, are prohibited where potassium sulfide is used, handled, or stored in a manner that could create a potential fire or explosion hazard. Protect storage against physical damage. Shipping: Anhydrous potassium sulfide requires a shipping label of “SPONTANEOUSLY COMBUSTIBLE.” It falls in Hazard Class 4.2 and Packing Group II. Potassium sulfide, hydrated with not ,30% water of crystallization requires a shipping label of “CORROSIVE.” It falls in Hazard Class 8 and Packing Group II. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be
properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible solid. Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Poisonous gases are produced in fire, including hydrogen sulfide and sulfur oxides. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are selfcontained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positivepressure mode. Reference New Jersey Department of Health and Senior Services. (March 2001). Hazardous Substances Fact Sheet: Potassium Sulfide. Trenton, NJ
Procarbazine & procarbazine hydrochloride P:1020 Molecular Formula: C12H19N3O Common Formula: CH3NHNHCH2C6H4CONHCH(CH3)2 Synonyms: Ibenzmethyzine; 2-(p-Isopropyl carbamoyl benzyl)-1-methylhydrazine; N-Isopropyl-α-(2-methylhydrazino)-p-toluamide N isopropyl; Matulane; 4-[(2-Methylhydrazino)methyl]-N-isopropylbenzamide; 1-[Methyl-2(-isopropylcarbamoyl)benzyl]hydrazine; MIH; Natulan; NSC-77213; PCB; RO 4-6467 hydrochloride: Ibenzmethyzine hydrochloride; Ibenzmethyzin hydrochloride; IBZ; 1-(p-Isopropylcarbamoylbenzyl)-2-methylhydrazine hydrochloride; 2-[p-(Isopropylcarbamoyl)benzyl]-1-methylhydrazine hydrochloride; N-Isopropyl-p-(2-methylhydrazinomethyl)benzamidehydrochloride; N-Isopropyl-α-(2-methylhydrazino)-p-toluamide hydrochloride; Matulane; MBH; N-(1-Methylethyl)-4-[(2methylhydrazino)methyl]benzamide monohydrochloride; p(N0 -Methylhydrazinomethyl)-N-isopropylbenzamide hydrochloride; 1-Methyl-2-p-(isopropylcarbamoyl)-benzohydrazine hydrochloride; 1-Methyl-2-(p-isopropylcarbamoylbenzyl)hydrazine hydrochloride; MIH hydrochloride; Nathulane; Natulan; Natulanar; Natulan hydrochloride; NCI-C01810; NSC-77213; PCBhydrochloride; Procarbazin (German); RO 4-6467 CAS Registry Number: 671-16-9; 366-70-1 (hydrochloride) RTECS® Number: XS4550000; XS472000 (hydrochloride) UN/NA & ERG Number: UN2811 (toxic solid, organic, n.o.s.)/154
Procarbazine & procarbazine hydrochloride EC Number: 211-582-2; 206-678-6 (hydrochloride) Regulatory Authority and Advisory Bodies Carcinogenicity: IARC: (hydrochloride) Animal Sufficient Evidence; Human Limited Evidence, probably carcinogenic to humans, Group 2A, 1998; NTP: Reasonably anticipated to be a human carcinogen; NTP: Report on Carcinogens, 2004; NCI: Carcinogenesis Studies (ipr); clear evidence: mouse, rat 1979. California Proposition 65 Chemical: Cancer (methylhydrazine and its salts) 7/1/92; (procarbazine) 1/1/88; (procarbazine hydrochloride) cancer 1/1/88; Developmental/ Reproductive toxin 7/1/90. WGK (German Aquatic Hazard Class): No value assigned. Description: Procarbazine is a white to pale yellow crystalline powder with a slight odor. Molecular weight 5 221.34. The hydrochloride has a similar description. Molecular weight 5 257.80; Freezing/Melting point 5 223236 C (hydrochloride). Soluble in water. Potential Exposure: Procarbazine is available in capsule form. The primary use of this drug is as an antineoplastic agent in the treatment of advanced Hodgkin’s disease and oat-cell carcinoma of the lung. The hydrochloride compound is used in treatment. The FDA approved use of procarbazine hydrochloride in 1969 and indicated that the drug should be used as an adjunct to standard therapy. Possible exposure occurs during manufacture of the drug and direct exposure during its subsequent administration to patients. Some of the metabolites of procarbazine hydrochloride are both carcinostatic and carcinogenic. Incompatibilities: When heated to decomposition, it produces hydrogen chloride and nitrogen oxides. Incompatible with strong acids, strong alkalies. Permissible Exposure Limits in Air: No standard set. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Laboratory exposure of animals to procarbazine was studied by IP (intraperitoneal) injection. In rats, malignant lymphoma, adenocarcinoma of the mammary gland, and olfactory neuroblastomas were induced in statistically significant numbers. In mice, malignant lymphoma or leukemia, olfactory neuroblastomas, alveolar/ bronchiolar adenoma, and adenocarcinoma of the uterus were induced in statistically significant numbers. Can cause nausea, vomiting, diarrhea, stomach pain, loss of appetite, and weight loss. Symptoms of exposure include[52]: nausea, vomiting, anorexia, dry mouth, dysphagia, diarrhea, constipation, chills and fever, sweating, weakness, edema, cough, dermatitis, jaundice, headache, insomnia, coma. Long Term Exposure: A probable human carcinogen. There is some evidence that it causes cancer of the nervous system, blood-forming organs, breast, lung, uterus, and blood or bone marrow in humans. It has been shown to cause cancer in the same sites in animals. May damage the testes. The hydrochloride is a teratogen in animals and may decrease the body’s ability to produce blood cells, causing
2233
reduced white blood cells with increased infection and general weakness, reduced platelets, causing bleeding when cut or bruised, and/or reduced blood cells (anemia). Points of Attack: Blood. Medical Surveillance: Complete blood count (CBC). First Aid: Skin Contact[52]: Flood all areas of body that have contacted the substance with water. Do not wait to remove contaminated clothing; do it under the water stream. Use soap to help assure removal. Isolate contaminated clothing when removed to prevent contact by others. Eye Contact: Remove any contact lenses at once. Flush eyes well with copious quantities of water or normal saline for at least 2030 min. Seek medical attention. Inhalation: Leave contaminated area immediately; breathe fresh air. Proper respiratory protection must be supplied to any rescuers. If coughing, difficult breathing, or any other symptoms develop, seek medical attention at once, even if symptoms develop many hours after exposure. Ingestion: If convulsions are not present, give a glass or two of water or mild to dilute the substance. Assure that the person’s airway is unobstructed and contact a hospital or poison center immediately for advice on whether or not to induce vomiting. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in a refrigerator or in a cool, dry place. A regulated, marked area should be established where this chemical is handled, used, or stored in compliance with OSHA Standard 1910.1045. Shipping: Toxic solids, organic, n.o.s. require a shipping label of “POISONOUS/TOXIC MATERIALS.” They fall in Hazard Class 6.1. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is
2234
Promecarb
complete. Remove all ignition sources. Dampen spilled material with water to avoid dust, than transfer material to a suitable container. Use absorbent dampened with water to pick up remaining material. Wash surfaces well with soap and water. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible solid. Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Poisonous gases are produced in fire. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. References National Cancer Institute. (1979). Bioassay of Procarbazine for Possible Carcinogenicity, DHHS Publication No. (NIH) 79-819. Springfield, VA: National Technical Information Service New Jersey Department of Health and Senior Services. (August 2002). Hazardous Substances Fact Sheet: Procarbazine Hydrochloride. Trenton, NJ
Promecarb
P:1030
Molecular Formula: C12H17NO2 Common Formula: C6H3(CH3)(OCONHCH3)CH(CH3)2 Synonyms: Carbamic acid, methyl-, m-cym-5-yl ester; Carbamic acid, 3-methyl-5-(1-methylethyl)phenyl-, methyl ester; Carbamic acid, N-methyl-, 3-methyl-5-isopropropylphenyl ester; Carbamult; Carbanilic acid, 3-isopropyl-5methyl-, methyl ester; m-cym-5-yl-methylcarbamate; ENT27,300; ENT 27,300-A; EP316; 3-Isopropyl-5-methylcarbamic acid methyl ester; 3-Isopropyl-5-methylphenyl N-methylcarbamate; 5-Isopropyl-m-tolyl methyl-carbamate; Methylcarbamic acid m-cym-5-yl ester; N-Methylcarbamic acid 3-methyl-5-isopropylphenyl ester; 5-Methyl m-cumenyl methylcarbamate; 3-Methyl-5-isopropyl-N-methyl carbamate; (3-Methyl-5-isopropylphenyl)-N-methylcarbamat (German); 3-Methyl-5-isopropylphenyl-N-methyl carbamate;
3-Methyl-5-(1-methylethyl)phenol methylcarbamate; 3Methyl-5-(1-methylethyl)phenyl-carbamic acid methyl ester; Minacide; Morton EP-316; Phenol, 3-methyl-5-(1-methylethyl)-, methylcarbamate; Schering 34615; UC 9880; Union Carbide UC-9880 CAS Registry Number: 2631-37-0 RTECS® Number: FB8050000 UN/NA & ERG Number: UN2757/151 EC Number: 220-113-0 [Annex I Index No.: 006-037-00-9] Regulatory Authority and Advisory Bodies US EPA Hazardous Waste Number (RCRA No.): P201. Superfund/EPCRA [40CFR 302 and 355, F R: 8/16/06,Vol 71, No. 158] Reportable Quantity (RQ): 1000 lb (454 kg). RCRA, 40CFR261, Appendix 8 Hazardous Constituents. RCRA 40CFR268.48; 61FR15654, Universal Treatment Standards: Wastewater (mg/L), 0.056; Nonwastewater (mg/ kg), 1.4 Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 500/10,000 lb (227/4540 kg). Reportable Quantity (RQ): 1000 lb (454 kg). US DOT Regulated Marine Pollutant (49CFR172.101, Appendix B). European/International Regulations: Hazard Symbol: T, N; Risk phrases: R25; R50/53; Safety phrases: S1/2; S24; S37; 45; S60; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): 3—Severe hazard to waters. Description: Promecarb is a colorless, odorless, crystalline solid. Molecular weight 5 207.30; Freezing/Melting point 5 8788 C. Hazard Identification (based on NFPA704 M Rating System): Health 3, Flammability 1, Reactivity 1. Slightly soluble in water. Potential Exposure: Those involved in the manufacture, formulation, or application of this nonsystemic contact insecticide. Incompatibilities: Alkalis. Permissible Exposure Limits in Air Protective Action Criteria (PAC) TEEL-0: 3 mg/m3 PAC-1: 10 mg/m3 PAC-2: 16 mg/m3 PAC-3: 25 mg/m3 Determination in Water: Fish Tox 5 33.48370000 ppb (INTERMEDIATE). Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Promecarb is highly toxic by ingestion and is absorbed through the intact skin. It is a reversible cholinesterase inhibitor and its effects are related to action on the nervous system. Diarrhea, nausea, vomiting, excessive salivation, headache, pinpoint pupils, and uncoordinated muscle movements are all common symptoms of exposure to carbamate insecticides. Long Term Exposure: Cholinesterase inhibitor; cumulative effect is possible. This chemical may damage the nervous
Promecarb system with repeated exposure, resulting in convulsions, respiratory failure. May cause liver damage. Human Tox; 350.00000 ppb (VERY LOW). Points of Attack: Respiratory system, lungs, central nervous system, cardiovascular system, skin, eyes, plasma and red blood cell cholinesterase. Medical Surveillance: Before employment and at regular times after that, the following are recommended: plasma and red blood cell cholinesterase levels (tests for the enzyme poisoned by this chemical). If exposure stops, plasma levels return to normal in 12 weeks while red blood cell levels may be reduced for 13 months. When cholinesterase enzyme levels are reduced by 25% or more below preemployment levels, risk of poisoning is increased, even if results are in lower ranges of “normal.” Reassignment to work not involving carbamate pesticides is recommended until enzyme levels recover. If symptoms develop or overexposure occurs, repeat the above tests as soon as possible and get an examination of the nervous system. Also, consider complete blood count. Consider chest X-ray following acute overexposure. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode.
2235
Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, wellventilated area away from alkaline materials. Shipping: Promecarb falls into the class of Carbamate pesticides, solid, toxic, n.o.s. This compound requires a shipping label of “POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 6.1 and Packing Group III. Spill Handling: Keep unnecessary people away; isolate hazard areas and deny entry. Stay upwind and keep out of low areas. Do not touch spilled material or breathe the dusts, vapors, or fumes from burning materials. Use water spray to reduce vapors. Do not handle broken packages without protective equipment. Wash away any material that may have contacted the body with soap and water. Take up small spills with sand or other noncombustible absorbent material and place in containers for later disposal. Small dry spills: with clean shovel place material into clean, dry container and cover; move containers from spill area. Dike far ahead of large spills for later disposal. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Soil Adsorption Index (Koc) 5 200 (estimate). Fire Extinguishing: Extinguish fire using an agent suitable for the surrounding fire, as the material itself burns with difficulty. Use water in flooding quantities as a fog. Use alcohol foam, carbon dioxide, or dry chemical. Poisonous gases are produced in fire. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Small quantities: treat with alkali and then bury. Large quantities: incineration.[22] In accordance with 40CFR165, follow recommendations for the disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by contacting your local or federal environmental control agency or by contacting your regional EPA office.
2236
Pronamide
Reference US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Promecarb. Washington, DC: Chemical Emergency Preparedness Program
Pronamide
P:1040
Molecular Formula: C12H11Cl2NO Synonyms: Benzamide, 3,5-dichloro-N-(1,1-dimethyl-2propynyl); Campbell’s Rapier; 3,5-Dichloro-N-(1,1dimethyl-2-propynyl)benzamide; 3,5-Dichloro-N-(1,1-dimethylprop-2-ynyl)benzamide; 3,5-Dichloro-N-(1,1-dimethylpropynyl) benzamide; N-(1,1-Dimethylpropynyl)-3,5dichlorobenzamide; Kerb; Kerb50W; Kerb propyzamide 50; Propyzamide; Rapier CAS Registry Number: 23950-58-5 RTECS® Number: CV3460000 UN/NA & ERG Number: UN3077/171 EC Number: 245-951-4 [Annex I Index No.: 616-055-00-4] Regulatory Authority and Advisory Bodies Banned or Severely Restricted (USA) (UN).[13] US EPA Hazardous Waste Number (RCRA No.): U192. RCRA, 40CFR261, Appendix 8 Hazardous Constituents. RCRA 40CFR268.48; 61FR15654, Universal Treatment Standards: Wastewater (mg/L), 0.093; Nonwastewater (mg/kg), 1.5. RCRA 40CFR264, Appendix 9; TSD Facilities Ground Water Monitoring List. Suggested test method(s) (PQL μg/L): 8270 (10). EPCRA Section 313 Form R de minimis concentration reporting level: 1.0%. California Proposition 65 Chemical: Cancer 5/1/96. Hazard Symbols: Xn, N, Risk phrases: R40; R50/53, Safety phrases: S36/37; S60; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): No value assigned. Description: Pronamide is a colorless crystalline solid. Molecular weight 5 256.14; Freezing/Melting point 5 155156 C; Vapor pressure 5 0.0001 mmHg at 25 C. Insoluble in water; solubility 5 15 mg/L. Potential Exposure: Those involved in the manufacture, formulation, and application of this selective herbicide. Permissible Exposure Limits in Air No standards or TEEL available. Permissible Concentration in Water: The EPA has derived a lifetime health advisory of 0.052 mg/L (52 μg/L). Determination in Water: Extraction with methylene chloride, separation by capillary-column gas chromatography; then measurement using a nitrogenphosphorus detector. Fish Tox 5 13901.63079000 ppb (VERY LOW). Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Eye contact can cause irritation. Inhalation can cause irritation of the respiratory tract with
cough, phlegm, and/or chest tightness. The acute oral LD50 for male rats is 8350 mg/kg and for female rats is 5620 mg/ kg (insignificantly toxic in both cases). Long Term Exposure: Applying the criteria described in EPA’s final guidelines for assessment of carcinogenic risk, pronamide has tentatively been classified in Group C: possible human carcinogen. This category is for substances with limited evidence of carcinogenicity in animals in the absence of human data. There is limited animal evidence of liver cancer. Human Tox 5 22.72727 ppb (INTERMEDIATE). Points of Attack: Cancer site in animals: liver. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—Green: General storage may be used. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, well-ventilated area away from strong oxidizers. Where possible, automatically transfer material from drums or other storage containers to process containers. A regulated, marked area should be established where this chemical is handled, used, or stored in compliance with OSHA Standard 1910.1045.
Propachlor Shipping: The name of this material is not on the DOT list of materials[19] for label and packaging standards. However, based on regulations, it may be classified[52] as an Environmentally hazardous substances, solid, n.o.s. This chemical requires a shipping label of “CLASS 9.” It falls in Hazard Class 9 and Packing Group III.[20, 21] Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Use HEPA vacuum or wet method to reduce dust during cleanup. Do not dry sweep. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Soil Adsorption Index (Koc) 5 200. Fire Extinguishing: This chemical is a combustible solid. Use dry chemical, carbon dioxide, or water spray extinguishers. Poisonous gases are produced in fire, including hydrogen chloride and oxides of nitrogen. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are selfcontained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positivepressure mode. Disposal Method Suggested: Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant ($100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. In accordance with 40CFR165, follow recommendations for the disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by contacting your local or federal environmental control agency or by contacting your regional EPA office. References US Environmental Protection Agency. (August 1987). Health Advisory: Pronamide. Washington, DC: Office of Drinking Water New Jersey Department of Health and Senior Services. (July 2005). Hazardous Substances Fact Sheet: Pronamide. Trenton, NJ
Propachlor
2237
P:1045
Molecular Formula: C11H14ClNO Common Formula: (ClCH2CO)N(C6H5)CH(CH3)2 Synonyms: Acetamide, 2-chloro-N-isopropyl-; Acetamide, 2-chloro-N-(1-methylethyl)-N-phenyl-; Aclid; AI3-51503; Albrass; Bexton; Bexton 4L; Chloressigsaeure-N-isopropylanilid (German); α-Chloro-N-isopropylacetanilide; 2-Chloro-N-isopropylacetanilide; 2-Chloro-N-isopropyl-Nphenylacetamide; 2-Chloro-N-(1-methylethyl)-N-phenylacetamide; CIPA; CP31393; N-Isopropyl-α-chloroacetanilide; N-Isopropyl-2-chloroacetanilide; Niticid; Propachlore; Propacloro (Spanish); Ramrod; Ramrod 65; Satecid CAS Registry Number: 1918-16-7 RTECS® Number: AE1575000 UN/NA & ERG Number: UN2588/151 EC Number: 217-638-2 [Annex I Index No.: 616-008-00-8] Regulatory Authority and Advisory Bodies Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. EPCRA Section 313 Form R de minimis concentration reporting level: 1.0%. California Proposition 65 Chemical: Cancer 2/27/01. European/International Regulations: Hazard Symbol: Xn, N; Risk phrases: R22; R36; R43; R50/53; Safety phrases: S2; S24; S37; S60; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): No value assigned. Description: Propachlor is a light tan solid. Molecular weight 5 211.71; Boiling point 5 110 C at 0.03 mm; Freezing/Melting point 5 6776 C; Flash point 5 about 316 C. Slightly soluble in water. Potential Exposure: Those engaged in the manufacture, formulation, and application of this preemergence herbicide, which is used to combat annual grasses and broadleaved weeds in corn, soybeans, cotton, sugar cane, and vegetable crops. Incompatibilities: Incompatible with alkaline materials, strong acids; strong oxidizers. Attacks carbon steel. Permissible Exposure Limits in Air Russia[35, 43] set a MAC of 0.5 mg/m3 in work-place air. Permissible Concentration in Water: Russia[35, 43] set a MAC of 0.01 mg/L in water bodies used for domestic purposes and of zero in water for fishery purposes. The EPA has set a lifetime health advisory of 0.092 mg/L (92 μg/L). States which have set guidelines for propachlor in drinking water include Kansas at 700 μg/L and Maine at 200 μg/L. Determination in Water: Fish Tox 5 17.92643000 ppb MATC (INTERMEDIATE). Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: The maximal tolerated dosage of propachlor without adverse effect is reported as 133.3 mg/ kg/day in both rats and dogs. Other workers reported slight organ pathology in rats, mice, and rabbits at 100 mg/kg/day
2238
Propadiene
or higher; this agrees approximately with the former data. Apparently, no long-term toxicity studies have been completed that would contribute information on reproductive effects or carcinogenic potential of propachlor or its degradation products, which include aniline derivatives. These studies are needed. Long Term Exposure: May be a mutagen. Human Tox 5 10.93750 ppb; Chronic Human Carcinogen Level (INTERMEDIATE). First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, well-ventilated area away from strong oxidizers. Where possible, automatically transfer material from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of this chemical should be grounded and bonded. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings.
Shipping: Pesticides, solid, toxic, n.o.s. require a shipping label of “POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 6.1 and Packing Group III. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Soil Adsorption Index (Koc) 5 80. Fire Extinguishing: This chemical is a combustible solid. Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Poisonous gases are produced in fire, including nitrogen oxides and chlorine. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Alkaline hydrolysis would yield N-isopropylaniline. However, incineration at 850 C together with flue gas scrubbing is the preferred disposal method.[22] References US Environmental Protection Agency. (August 1987). Health Advisory: Propachlor. Washington, DC: Office of Drinking Water US Environmental Protection Agency. Integrated Risk Information System (IRIS) Propachlor. Washington, DC. Various dates. ,http://www.epa.gov/IRIS/subst/0096.htm.
Propadiene
P:1050
Molecular Formula: C3H4 Common Formula: H2CQCQCH2 Synonyms: Allene; Allylenel; Dimethylenemethane; 1,2Propadiene; Propadieno (Spanish) CAS Registry Number: 463-49-0 RTECS® Number: BA040000 UN/NA & ERG Number: UN2200/116 EC Number: 207-335-3 (allene)
Propadiene Regulatory Authority and Advisory Bodies Department of Homeland Security Screening Threshold Quantity (pounds): Release hazard 10,000 ($1.00% concentration). Clean Air Act: Accidental Release Prevention/Flammable Substances, (Section 112[r], Table 3), TQ 5 10,000 lb (4540 kg). European/International Regulations: not listed in Annex 1. WGK (German Aquatic Hazard Class): No value assigned. Description: Propadiene is a colorless, flammable gas or liquid with a sweet odor. Molecular weight 5 40.07; Boiling point 5 32 C; Freezing/Melting point 5 137 C. Explosive limits: LEL 5 2.1%; UEL—unknown. Hazard Identification (based on NFPA-704 M Rating System): Health 2, Flammability 4, Reactivity 3. Insoluble in water. Potential Exposure: Used in chemical synthesis and as a component in mixtures with methyl acetylene, which make up specialty welding gases. Incompatibilities: Violent reaction with strong oxidizers, strong acids, nitrogen oxides. Permissible Exposure Limits in Air Protective Action Criteria (PAC) TEEL-0: 40 ppm PAC-1: 125 ppm PAC-2: 750 ppm PAC-3: 4000 ppm Determination in Air: Use NIOSH Analytical Method (IV) #1500, Hydrocarbons. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Propadiene can affect you when breathed in. Exposure can cause irritation of the eyes, nose, and throat. Very high levels can cause you to feel dizzy, lightheaded, and to pass out. Extremely high levels could cause death. Contact with the liquid may cause frostbite. Long Term Exposure: Unknown at this time. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. If frostbite has occurred, seek medical attention immediately; do NOT rub the affected areas or flush them with water. In order to prevent further tissue damage, do NOT attempt to remove frozen clothing from frostbitten areas. If frostbite has NOT occurred, immediately and thoroughly wash contaminated skin with soap and water.
2239
Personal Protective Methods: Wear appropriate personal protective clothing to prevent the skin from becoming frozen from contact with the evaporating liquid or from contact with vessels containing the liquid. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear gas-proof goggles unless full facepiece respiratory protection is worn. Wear splash-proof chemical goggles and face shield when working with liquid unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Where there is potential for exposures to propadiene, use a NIOSH/MSHA- or European Standard EN149-approved supplied-air respirator with a full facepiece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuous-flow mode; or use a NIOSH/MSHA- or European Standard EN149approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positivepressure mode. Storage: Color Code—Red Stripe: Flammability Hazard: Store separately from all other flammable materials. Prior to working with this chemical you should be trained on its proper handling and storage. Before entering confined space where this chemical may be present, check to make sure that an explosive concentration does not exist. Propadiene must be stored to avoid contact with strong oxidizers (such as chlorine, bromine, and fluorine), strong acids (such as hydrochloric, sulfuric, and nitric), and nitrogen oxides since violent reactions occur. Sources of ignition, such as smoking and open flames, are prohibited where propadiene is handled, used, or stored. Wherever propadiene is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Store cylinders in well-ventilated areas away from potential heat sources. Protect cylinders from physical damage. Procedures for the handling, use, and storage of cylinders should be in compliance with OSHA 1910.101 and 1910.169, as with the recommendations of the Compressed Gas Association. Shipping: Propadiene, inhibited, requires a shipping label of “FLAMMABLE GAS.” It falls in Hazard Class 2.1. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Establish forced ventilation to keep levels below explosive limit. Ventilate area of leak to disperse the gas. Stop the flow of gas if it can be done safely. If source of leak is a cylinder and the leak cannot be stopped in place, remove leaking cylinder to a safe place in the open air, and repair leak or allow cylinder to empty. Keep this chemical out of confined space, such as a sewer, because of the possibility of an explosion,
2240
Propane
unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a flammable gas. Poisonous gases are produced in fire. Do not extinguish the fire unless the flow of gas can be stopped and any remaining gas is out of the line. Specially trained personnel may use fog lines to cool exposures and let the fire burn itself out. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If cylinders are exposed to excessive heat from fire or flame contact, withdraw immediately to a secure location. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Reference New Jersey Department of Health and Senior Services. (February 2001). Hazardous Substances Fact Sheet: Propadiene. Trenton, NJ
Propane
P:1060
Molecular Formula: C3H8 Common Formula: CH3CH2CH3 Synonyms: A-108; Dimethylmethane; Hydrocarbon propellent A-108; n-Propane; Propano (Spanish); Propyl hydride CAS Registry Number: 74-98-6 RTECS® Number: TX2275000 UN/NA & ERG Number: UN1978/115; UN1075 (liquefied)/115 EC Number: 200-827-9 [Annex I Index No.: 601-003-00-5] Regulatory Authority and Advisory Bodies Department of Homeland Security Screening Threshold Quantity (pounds): Release hazard 60,000. Note: Facilities are not required to count propane in tanks of 10,000 lb or less. The higher threshold of 60,000 lb is set to focus on the screening of high-volume propane users; not on nonindustrial propane users.
Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Clean Air Act: Accidental Release Prevention/Flammable Substances, (Section 112[r], Table 3), TQ 5 10,000 lb (4540 kg). European/International Regulations: Hazard Symbol: F 1 ; Risk phrases: R12; Safety phrases: S2; S9; S16 (see Appendix 4). WGK (German Aquatic Hazard Class): Nonwater polluting agent. Description: Propane is a colorless gas that is odorless when pure (a foul-smelling odorant is often added). The odor threshold is 2700 ppm. Molecular weight 5 44.11; Boiling point 5 42.2 C; Freezing/Melting point 5 187.8 C; Relative vapor density (air 5 1) 5 1.55; Vapor pressure 5 8.4 atm at 21; Flash point 5 flammable gas (104 C); Autoignition temperature 5 450 C. Explosive limits: LEL 5 2.1% C; UEL 5 9.5%. Hazard Identification (based on NFPA-704 M Rating System): Health 1, Flammability 4, Reactivity 0. Slightly soluble in water; solubility 5 0.01%. Potential Exposure: Compound Description: Agricultural Chemical. Propane is used as a household, industrial, and vehicle fuel; it is used as a refrigerant and aerosol propellant; it is used as an intermediate in petrochemical manufacture. Incompatibilities: Flammable gas. Strong oxidizers may cause fire and explosions. Liquid attacks some plastics, rubber, and coatings. Permissible Exposure Limits in Air Conversion factor: 1 ppm 5 1.80 mg/m3 at 25 C & 1 atm. OSHA PEL: 1000 ppm/1800 mg/m3 TWA. NIOSH REL: 1000 ppm/1800 mg/m3 TWA. ACGIH TLV®[1]: 1000 ppm TWA as aliphatic hydrocarbon gas (C1C4). NIOSH IDLH: 2100 ppm [LEL]. Protective Action Criteria (PAC)* TEEL-0: 1000 ppm PAC-1: 5500 ppm PAC-2: 17,000 ppm PAC-3: 33,000 ppm *AEGLs (Acute Emergency Guideline Levels) & ERPGs (Emergency Response Planning Guideline) are in bold face. DFG MAK: 1000 ppm/1800 mg/m3 TWA; Peak Limitation Category II(4); Pregnancy Risk Group D. Australia: asphyxiant, 1993; Austria: MAK 1000 ppm (1800 mg/m3), 1999; Belgium: asphyxiant, 1993; Denmark: TWA 1000 ppm (1800 mg/m3), 1999; Finland: TWA 800 ppm (1100 mg/m3), 1999; Hungary: asphyxiant, 1993; the Philippines: TWA 1000 ppm (1800 mg/m3), 1993; Switzerland: MAK-W 1000 ppm (1800 mg/m3), 1999; United Kingdom: asphyxiant, 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: TWA 2500 ppm. Determination in Air: By combustible gas meter NIOSH (II-2) Method #S-87; OSHA Analytical Methods PV-2077.
Propane Permissible Concentration in Water: No criteria set, but EPA[32] has suggested a permissible ambient goal of 120,000 μg/L based on health effects. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Very high levels may produce the following symptoms, primarily due to lack of oxygen: dizziness, lightheadedness, disorientation, headache, numbness, vomiting, unconsciousness, and death from suffocation. Narcotic at high levels. Contact with the liquid can cause frostbite. Long Term Exposure: No effects reported. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. If frostbite has occurred, seek medical attention immediately; do NOT rub the affected areas or flush them with water. In order to prevent further tissue damage, do NOT attempt to remove frozen clothing from frostbitten areas. If frostbite has NOT occurred, immediately and thoroughly wash contaminated skin with soap and water. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. Neoprene™, nitrile 1 PVC, Polyurethane, and polyethylene are among the recommended protective materials. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear gas-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: 2100 ppm: Sa (APF 5 10) (any supplied-air respirator) or SCBAF (APF 5 50) (any selfcontained breathing apparatus with a full face-piece). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd,Pp (APF 5 10,000) (any self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positivepressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure
2241
mode in combination with an auxiliary self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: SCBAE (any appropriate escape-type, self-contained breathing apparatus). Storage: Color Code—Red Stripe: Flammability Hazard: Store separately from all other flammable materials. Prior to working with this chemical you should be trained on its proper handling and storage. Before entering confined space where this chemical may be present, check to make sure that an explosive concentration is not a danger. Propane must be stored to avoid contact with strong oxidizers (such as chlorine, bromine, and fluorine) since violent reactions occur. Sources of ignition, such as smoking and open flames, are prohibited where propane is handled, or stored. Use only nonsparking tools and equipment, especially when opening and closing containers of propane. Wherever propane is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Procedures for the handling, use, and storage of cylinders should be in compliance with OSHA 1910.101 and 1910.169, as with the recommendations of the Compressed Gas Association. Shipping: Propane; or Petroleum gases, liquefied; or Liquefied petroleum gas Propane, requires a shipping label of “FLAMMABLE GAS.”LD50 5 (oral-rat). They fall in DOT Hazard Class 2.1. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Establish forced ventilation to keep levels below explosive limit. Stop the flow of gas if it can be done safely. If source of leak is a cylinder and the leak cannot be stopped in place, remove leaking cylinder to a safe place in the open air, and repair leak or allow cylinder to empty. Keep this chemical out of confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a flammable gas. Poisonous gases are produced in fire. Do not extinguish the fire unless the flow of gas can be stopped and any remaining gas is out of the line. Specially trained personnel may use fog lines to cool exposures and let the fire burn itself out. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed
2242
Propane sultone
containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If cylinders are exposed to excessive heat from fire or flame contact, withdraw immediately to a secure location. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Dissolve or mix the material with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber. All federal, state, and local environmental regulations must be observed. References New York State Department of Health. (February 1986). Chemical Fact Sheet: Propane. Albany, NY: Bureau of Toxic Substance Assessment New Jersey Department of Health and Senior Services. (May 2004). Hazardous Substances Fact Sheet: Propane. Trenton, NJ
Propane sultone
P:1070
Molecular Formula: C3H6O3S Synonyms: 3-Hydroxy-1-propanesulphonic acid sultone; 3Hydroxy-1-propanesulphonic acid γ-sultone; 3-Hydroxy-1propanesulphonic acid sulfone; 1,2-Oxathrolane 2,2-dioxide; 1-propanesulfonic acid-3-hydroxy-g-sultone; 1,3-Propanesultone; 1,2-Oxathiolane 2,2-dioxide; 1-Propanesulfonic acid-3-hydroxy-g-sulfone; Propane sultone CAS Registry Number: 1120-71-4 RTECS® Number: RP5425000 UN/NA & ERG Number: UN2811 (toxic solid, organic, n.o.s.)/154 EC Number: 214-317-9 [Annex I Index No.: 016-032-00-3] Regulatory Authority and Advisory Bodies Carcinogenicity: NTP: 11th Report on Carcinogens, 2004: Reasonably anticipated to be a human carcinogen; IARC: Human No Adequate Data, Animal Sufficient Evidence, possibly carcinogenic to humans, Group 2B, 1999; NIOSH: Potential occupational carcinogen. US EPA Gene-Tox Program, Positive: Carcinogenicity— mouse/rat EPA; Positive: Cell transform.—RLV F344 rat embryo EPA; Positive: Cell transform.—SA7/SHE; Hostmediated assay EPA; Positive: E. coli polA without S9; Histidine reversion—Ames test EPA; Positive: S. cerevisiae gene conversion; S. cerevisiae—homozygosis EPA; Positive: S. pombe—reversion EPA; Positive/dose response: In vitro SCE—nonhuman EPA; Positive/dose response: In vitro UDS—human fibroblast EPA; Inconclusive: SHE— clonal assay. Banned or Severely Restricted (Sweden) (UN).[13]
Very Toxic Substance (World Bank).[15] Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Clean Air Act: Hazardous Air Pollutants (Title I, Part A, Section 112). US EPA Hazardous Waste Number (RCRA No.): U193. RCRA, 40CFR261, Appendix 8 Hazardous Constituents. Reportable Quantity (RQ): 10 lb (4.54 kg). EPCRA Section 313 Form R de minimis concentration reporting level: 0.1%. California Proposition 65 Chemical: Cancer 1/1/88. Canada, WHMIS, Ingredients Disclosure List Concentration 0.1%. European/International Regulations: Hazard Symbol: T; Risk phrases: R45; R21/22; Safety phrases: S53; S45 (see Appendix 4). WGK (German Aquatic Hazard Class): 3—Severe hazard to waters. Description: Propane sultone is a white crystalline solid or a colorless liquid above 30 C. It releases a foul odor as it melts. Molecular weight 5 122.15; Specific gravity (H2O:1) 5 1.39 at 25 C; Boiling point 5 180 C at 30 mm; 155157 C at 14 mm; Freezing/Melting point 5 31 C; Flash point .113 C.[50] Hazard Identification (based on NFPA-704 M Rating System): Health 2, Flammability 1, Reactivity 0. Soluble in water; solubility 5 10%. Potential Exposure: Compound Description: Tumorigen, Mutagen; Reproductive Effector; Primary Irritant. Those involved in use of this chemical intermediate to introduce the sulfopropyl group (aCH2CH2CH2SO3a) into molecules of other products. Incompatibilities: Strong oxidizers. Permissible Exposure Limits in Air OSHA PEL: None. NIOSH REL: A potential occupational carcinogen. [skin]; Limit exposure to lowest feasible concentration. See NIOSH Pocket Guide, Appendix A. ACGIH TLV®[1]: Exposures by all routes should be carefully controlled to levels as low as possible. Confirmed animal carcinogen with unknown relevance to humans. Protective Action Criteria (PAC) TEEL-0: 0.15 mg/m3 PAC-1: 0.5 mg/m3 PAC-2: 3.5 mg/m3 PAC-3: 250 mg/m3 DFG MAK: [skin] Carcinogen Category 2. NIOSH IDLH: Not determined. Potential occupational carcinogen. Austria [skin], carcinogen, 1999; Switzerland: carcinogen, 1999; United Kingdom: carcinogen, 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: confirmed animal carcinogen with unknown relevance to humans. Several states have set guidelines or standards for propane sultone in ambient air[60] ranging from zero (North Dakota) to 0.03 μg/m3 (New York) to 3.0 μg/m3 (Virginia).
Propanil Routes of Entry: Inhalation, skin absorption, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Irritates the eyes, skin, and respiratory system. More irritating if heated. Long Term Exposure: Potential occupational carcinogen. Other long-term effects are unknown at this time. Points of Attack: Eyes, skin, respiratory system. Cancer site in animals: skin, blood or bone marrow, brain or spine. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield when working with liquid unless full face-piece respiratory protection is worn. Wear dust-proof goggles and face shield when working with powders or dust unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: At any detectable concentration: SCBAF: Pd,Pp (APF 5 10,000) (any NIOSH/MSHA- or European Standard EN 149-approved self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressuredemand or other positive-pressure mode in combination with an auxiliary, self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: GmFOv100 (APF 5 50) [any air-purifying, fullface-piece respirator (gas mask) with a chin-style, front- or back-mounted organic vapor canister having an N100, R100, or P100 filter] or SCBAE (any appropriate escapetype, self-contained breathing apparatus). Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool,
2243
well-ventilated area away from strong oxidizers. Where possible, automatically transfer material from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of this chemical should be grounded and bonded. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. A regulated, marked area should be established where this chemical is handled, used, or stored in compliance with OSHA Standard 1910.1045. Shipping: Toxic solids, organic, n.o.s. require a shipping label of “POISONOUS/TOXIC MATERIALS.” They fall in Hazard Class 6.1. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible solid. Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Poisonous gases are produced in fire, including sulfur oxides. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosionproof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. References Sax, N. I. (Ed.). (1984). Dangerous Properties of Industrial Materials Report, 4, No. 3, 8285 New Jersey Department of Health and Senior Services. (June 2000). Hazardous Substances Fact Sheet: 1,2Oxathiolane-2,2-Dioxide. Trenton, NJ
Propanil
P:1080
Molecular Formula: C9H9Cl2NO Common Formula: Cl2C6H3NHCOC2H5 Synonyms: AI3-31382; BAY 30130; Chem rice; Crystal propanil-4; DCPA; N-(3,4-Dichlorophenyl)propanamide;
2244
Propanil
30 ,40 -Dichlorophenylpropionanilide; 30 ,40 -Dichloropropionanilide; 3,4-Dichloropropionanilide; Dichloropropionanilide; Dipram; DPA; Farmco propanil; FW-734; Herbax technical; Montrose propanil; NSC31312; Propanamide, N(3,4-dichlorophenyl)-; Propanide; Propionanilide, 30 ,40 dichloro-; Propionic acid 3,4-dichloroanilide; Rogue; Stam; Stam LV10; Stam F-34; Stampede 3E; Stam supernox; Strel; Surpur; Synpran N; Vertac CAS Registry Number: 709-98-8; (alt.) 11096-32-5 RTECS® Number: UE4900000 DOT ID and ERG Number: UN3077/171 EC Number: 211-914-6 [Annex I Index No.: 616-009-00-3] Regulatory Authority and Advisory Bodies US EPA Gene-Tox Program, Positive: B. subtilis rec assay; 1988, Negative: Aspergillus—forward mutation; E. coli pol A without S9; 1988, Negative: Histidine reversion—Ames test; 1988, Negative: In vitro UDS—human fibroblast; TRP reversion; 1988, Negative: S. cerevisiae—homozygosis. US EPA, FIFRA, 1998 Status of Pesticides: Supported. Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Safe Drinking Water Act: Priority List (55 FR 1470) as DCPA (and its acid metabolites). EPCRA Section 313 Form R de minimis concentration reporting level: 1.0%. European/International Regulations: Hazard Symbol: Xn, N; Risk phrases: R22; R50; Safety phrases: S2; S22; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): 3—Severe hazard to waters. Description: Propanil is a colorless solid. The technical product is a brown crystalline solid. Molecular weight 5 218.09; Specific gravity (H2O:1) 5 1.22 at 25 C; Freezing/Melting point 5 9293 C (pure); 8891 C (technical grade); Freezing/Melting point (pure) 5 8992 C (pure); 8589 C (technical grade). Hazard Identification (based on NFPA-704 M Rating System): Health 2, Flammability 0, Reactivity 0. Insoluble in water. Commercial formulations use carrier solvents that may change the physical properties shown. Potential Exposure: Compound Description: Agricultural Chemical; Mutagen. Propanil is used as a postemergent herbicide for rice and spring wheat. Those involved in the manufacture, formulation, and application of this contact herbicide. Permissible Exposure Limits in Air No TEEL available. Russia[43] set a MAC of 0.1 mg/m3 in work-place air and has set a MAC value of 0.005 mg/m3 for ambient air in residential areas on a once-daily basis and 0.001 mg/m3 on a daily average basis. Permissible Concentration in Water: Russia[43] set a MAC of 0.1 mg/L in water bodies used for domestic purposes. Determination in Water: Fish Tox 5 0.48990000 ppb (EXTRA HIGH). Octanolwater coefficient: Log Kow 5 3.1.
Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Propanil is well tolerated by experimental animal on a chronic basis, and there is little or no indication of mutagenic or oncogenic properties of the compound. The highest no-adverse-effect concentration of propanil based on reproduction in the rat and acute, subchronic, and chronic studies in rats and dogs is 400 ppm in the diet. Based on this data, an ADI was calculated at 0.02 mg/kg/day. LD50 (oral-rat) 2756 mg/kg (male); 2343 mg/kg (female). Long Term Exposure: Human Tox 5 35.00000 ppb (INTERMEDIATE). First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—Green: General storage may be used. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, well-ventilated area. Shipping: This chemical requires a shipping label of “CLASS 9.” It falls in Hazard Class 9 and Packing Group III.[20, 21]
Propargyl alcohol Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Soil Adsorption Index (Koc) 5 149. Fire Extinguishing: This chemical is a combustible solid. Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Poisonous gases are produced in fire. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Hydrolysis in acidic or basic media yields the more toxic substance, 3,4-dichloraniline, and is not recommended. References US Environmental Protection Agency, Special Review and Reregistration Division Office of Pesticide Programs. (1998). Agency Status of Pesticides in Registration, Reregistration, and Special Review (Rainbow Report). Washington, DC
Propargyl alcohol
P:1090
Molecular Formula: C3H4O Common Formula: HCCCH2OH Synonyms: AI3-24359; Alcohol propargilico (Spanish); Ethynylcarbinol; Ethynyl methanol; 1-Hydroxy-2-propyne; 3-Hydroxy-1-propyne; Methanol, ethynyl-; Propiolic alcohol; 1-Propyne-3-ol; 3-Propynol; 2-Propynol; 2-Propyn-1ol; 1-Propyn-3-ol; Prop-2-yn-1-ol; 2-Propynyl alcohol; Propynyl alcohol CAS Registry Number: 107-19-7 RTECS® Number: UK5075000 UN/NA & ERG Number: UN2929/131 EC Number: 203-471-2 [Annex I Index No.: 603-078-00-X]
2245
Regulatory Authority and Advisory Bodies Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. US EPA Hazardous Waste Number (RCRA No.): P102. RCRA, 40CFR261, Appendix 8 Hazardous Constituents. Reportable Quantity (RQ): 1000 lb (454 kg). EPCRA Section 313 Form R de minimis concentration reporting level: 1.0%. Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: Hazard Symbol: T, N; Risk phrases: R10; R23/24/25; R34; R51/53; Safety phrases: S1/2; S26; S28; S36; S45; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): 2—Hazard to waters. Description: Propargyl alcohol is a colorless liquid with a geranium-like odor. Molecular weight 5 56.07; Specific gravity (H2O:1) 5 0.97 at 25 C; Boiling point 5 119.9 C; Freezing/Melting point 5 52 C; Flash point 5 36 C. Explosive limits: LEL 5 3.4%; UEL 5 70%. Hazard Identification (based on NFPA-704 M Rating System): Health 4, Flammability 3, Reactivity 3. Soluble in water. Potential Exposure: Compound Description: Agricultural Chemical; Tumorigen, Mutagen. Propargyl alcohol is used as a corrosion inhibitor, soil fumigant, solvent, stabilizer, and chemical intermediate. Incompatibilities: Violent reaction with phosphorus pentoxide, oxidizers. May polymerize under the influence of heat, oxidizers, peroxides, light. Attacks many plastics. Permissible Exposure Limits in Air Conversion factor: 1 ppm 5 2.29 mg/m3 at 25 C & 1 atm. OSHA PEL: None. NIOSH REL: 1 ppm/2 mg/m3 TWA [skin]. ACGIH TLV®[1]: 1 ppm/2.3 mg/m3 TWA [skin]. Protective Action Criteria (PAC)* TEEL-0: 1 ppm PAC-1: 2.5 ppm PAC-2: 16 ppm PAC-3: 74 ppm *AEGLs (Acute Emergency Guideline Levels) & ERPGs (Emergency Response Planning Guideline) are in bold face. DFG MAK: 2 ppm; 4.7 mg/m3 TWA; Peak Limitation Category I(2); [skin]; Pregnancy Risk Group D. Australia: TWA 1 ppm (2 mg/m3), [skin], 1993; Austria: MAK 2 ppm (9 mg/m3), [skin], 1999; Belgium: TWA 1 ppm (2.3 mg/m3), [skin], 1993; Denmark: TWA 1 ppm (2.5 mg/m3), [skin], 1999; Finland: TWA 1 ppm (2 mg/m3); STEL 3 ppm (6 mg/m3), [skin], 1999; France: VME 1 ppm (2 mg/m3), [skin], 1999; the Netherlands: MAC-TGG 2 mg/m3, [skin], 2003; the Philippines: TWA 1 ppm (1 mg/m3), [skin], 1993; Russia: STEL 1 mg/m3, 1993; Switzerland: MAK-W 1 ppm (2 mg/m3), [skin], 1999; United Kingdom: TWA 1 ppm (2.3 mg/m3); STEL 3 ppm, [skin], 2000: Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: TWA 1 ppm [skin].
2246
Propargyl alcohol
Determination in Air: Use OSHA Analytical Method 97. Routes of Entry: Inhalation, skin absorption, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Propargyl alcohol can affect you when breathed and by passing through skin. Irritates the eyes, skin, and respiratory tract. Contact can severely burn the eyes, causing permanent damage. Skin contact can irritate the skin and allow dangerous amounts to enter the body. Affects the central nervous system. Exposure can cause you to feel dizzy, lightheaded, and to have trouble concentrating. High exposures can cause liver and kidney damage, coma, and death. Long Term Exposure: Propargyl alcohol may damage the liver and kidneys. Points of Attack: Skin, respiratory system, central nervous system, liver, kidneys. Medical Surveillance: If symptoms develop or overexposure is suspected, the following may be useful: liver and kidney function tests. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode.
Storage: (1) Color Code—Red: Flammability Hazard: Store in a flammable liquid storage area or approved cabinet away from ignition sources and corrosive and reactive materials. (2) Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Before entering confined space where this chemical may be present, check to make sure that an explosive concentration is not a danger. Propargyl alcohol must be stored to avoid contact with alkalis, mercury(II) sulfate; oxidizing materials and phosphonic anhydride since violent reactions occur. Sources of ignition, such as smoking and open flames, are prohibited where propargyl alcohol is used, handled, or stored in a manner that could create a potential fire or explosion hazard. Metal containers involving the transfer of 5 gallons or more of propargyl alcohol should be grounded and bonded. Drums must be equipped with selfclosing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of Propargyl alcohol. Wherever propargyl alcohol is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: This compound requires a shipping label of “POISONOUS/TOXIC MATERIALS, FLAMMABLE LIQUID.” It falls in Hazard Class 6.1 and Packing Group II. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Establish forced ventilation to keep levels below explosive limit. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a flammable liquid. Poisonous gases, including nitrogen oxides and chlorine, are produced in fire. Use dry chemical, carbon dioxide, or alcohol foam extinguishers. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a
Propargyl bromide secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Dissolve or mix the material with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber. All federal, state, and local environmental regulations must be observed. Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant ($100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. Reference New Jersey Department of Health and Senior Services. (November 2004). Hazardous Substances Fact Sheet: Propargyl Alcohol. Trenton, NJ
Propargyl bromide
P:1100
Molecular Formula: C3H3Br Common Formula: BrCH2CQCH Synonyms: γ-Bromoallylene; 3-Bromopropyne; 3-Bromo1-propyne; Bromuro de propargilo (Spanish) CAS Registry Number: 106-96-7 RTECS® Number: UK4375000 UN/NA & ERG Number: UN2345/130 EC Number: 203-447-1 Regulatory Authority and Advisory Bodies Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 10 lb (4.54 kg). Reportable Quantity (RQ): 10 lb (4.54 kg). European/International Regulations: not listed in Annex 1. WGK (German Aquatic Hazard Class): 3—Severe hazard to waters. Description: Propargyl bromide is a colorless liquid with a sharp odor. Molecular weight 5 118.97; Boiling point 5 8990 C; Freezing/Melting point 5 261.07 C; Flash point 5 10 C; Autoignition temperature 5 324 C. Explosive limits: LEL 5 3.0%; UEL—unknown. Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 3, Reactivity 4. Insoluble in water. Potential Exposure: This material is used as a soil fumigant. Not registered as a pesticide in the United States. Incompatibilities: Violent reaction with oxidizers. Becomes shock- or heat-sensitive when mixed with trichloronitromethane or chloropicrin. Detonates when heated to 220 C,
2247
or when heated while confined. May explode on contact with copper, copper alloys, mercury, silver. Permissible Exposure Limits in Air AIHA WEEL: 0.1 ppm TWA [skin] Protective Action Criteria (PAC) TEEL-0: 0.03 mg/m3 PAC-1: 0.03 mg/m3 PAC-2: 0.03 mg/m3 PAC-3: 20 mg/m3 Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: This material is very poisonous if swallowed. If inhaled, may be harmful. Skin and eye contact may cause burns. Symptoms of exposure include skin irritation and tearing of the eyes. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Keep victim quiet and maintain normal body temperature. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—Red: Flammability Hazard: Store in a flammable liquid storage area or approved cabinet away from ignition sources and corrosive and reactive materials. Prior to working with this chemical you should be trained
2248
Propazine
on its proper handling and storage. Before entering confined space where this chemical may be present, check to make sure that an explosive concentration is not a danger. Store in tightly closed containers in a cool, well-ventilated area away from oxidizers and heat. Where possible, automatically pump liquid from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of 5 gallons or more of this chemical should be grounded and bonded. Drums must be equipped with self-closing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: This compound requires a shipping label of “FLAMMABLE LIQUID.” It falls in Hazard Class 3 and Packing Group II. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Establish forced ventilation to keep levels below explosive limit. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a flammable liquid. Poisonous gases, including bromine, are produced in fire. Wear self-contained breathing apparatus and full protective clothing. Move container from fire area if you can do it without risk. Use dry chemical, carbon dioxide, or foam extinguishers. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. Do not get water inside container. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and
equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Reference US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Propargyl Bromide. Washington, DC: Chemical Emergency Preparedness Program
Propazine
P:1110
Molecular Formula: C9H16ClN5 Synonyms: 2,4-bis(Isopropylamino)-6-chloro-s-triazine; 2,4-Bis(propylamino)-6-chlor-1,3,5-triazin (German); 2Chloro-4,6-bis(isopropylamino)-s-triazine; Gesamil®; ® MAXX-90; Milogard ; Plantulin; Primatol P; Propasin; Propazin; Prozinex CAS Registry Number: 139-40-2 RTECS® Number: XY5300000 UN/NA & ERG Number: UN2753/151 EC Number: 205-359-9 [Annex I Index No.: 613-067-00-1] Regulatory Authority and Advisory Bodies US EPA, FIFRA 1998 Status of Pesticides: Canceled. Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. European/International Regulations: Hazard Symbol: Xn, N; Risk phrases: R40; R50/53; Safety phrases: S2; S36/37; S60; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): No value assigned. Description: Propazine is a colorless crystalline solid. Molecular weight 5 229.75; Freezing/Melting point 5 214 C; Vapor pressure 5 1.3 3 10 2 7 mmHg at 20 C. Slightly soluble in water. Potential Exposure: Compound Description: Agricultural Chemical; Tumorigen; Reproductive Effector. Those involved in the manufacture, formulation, and application of this preemergence selective herbicide used to control annual broadleaf weeds and grasses. Permissible Exposure Limits in Air Russia[43] set a MAC of 5.0 mg/m3 in work-place air and a MAC of 0.04 mg/m3 in ambient air in residential areas both on a momentary and a daily average basis. Permissible Concentration in Water: Russia[43] set a MAC of 1.0 mg/L in water bodies used for domestic purposes. The US EPA has determined a lifetime health advisory of 0.014 mg/L (14 μg/L) (see “References” below). States which have set guidelines for propazine in drinking water[61] include Kansas at 325 μg/L and Maine at 93 μg/L. Determination in Water: Analysis of propazine is by a gas chromatographic (GC) method applicable to the determination of certain nitrogen- and phosphorus-containing pesticides in water samples. In this method, approximately 1 L of sample is extracted with methylene chloride. The extract
Propham is concentrated and the compounds are separated using capillary column GC. Measurement is made using a nitrogenphosphorus detector. The method detection limit has not been determined for propazine, but it is estimated that the detection limits for analytes included in this method are in the range of 0.12 μg/L. Fish Tox 5 938.12580000 ppb (VERY LOW). Octanolwater coefficient: Log Kow 5 2.9. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. May be absorbed by the skin. Harmful Effects and Symptoms Short Term Exposure: May cause eye irritation. Contact dermatitis was reported in workers involved in propazine manufacturing. Poisonous if ingested. No other information on the health effects of propazine in humans was found in the available literature. Long Term Exposure: May cause skin allergy. Human Tox 5 10.00000 ppb (INTERMEDIATE). Points of Attack: Skin. Medical Surveillance: Examination by a qualified allergist. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this
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chemical you should be trained on its proper handling and storage. Shipping: Triazine pesticides, solid, toxic, require a shipping label of “POISONOUS/TOXIC MATERIALS.” The Hazard Class is 6.1 and Packing Group is III. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Soil Adsorption Index (Koc) 5 154. Fire Extinguishing: This chemical is a combustible solid. Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Poisonous gases are produced in fire, including nitrogen oxides and chlorine. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Reference US Environmental Protection Agency. (August 1987). Health Advisory: Propazine. Washington, DC: Office of Drinking Water
Propham
P:1120
Molecular Formula: C10H13NO2 Common Formula: C6H5NHCOOCH(CH3)2 Synonyms: Ban-hoe; Beet-kleen; Carbanilic acid, isopropyl ester; Chem-hoe; IPPC; Isopropyl carbanilate; Isopropyl carbanilic acid ester; Isopropyl-N-phenyl-carbamat (German); o-Isopropyl-N-phenyl carbamate; Isopropyl phenylcarbamate; Isopropyl-N-phenyl carbamate; Isopropyl-Nphenyurethan (German) Ortho grass killer; NPhenylcarbamate d’isopropyle (French); Phenylcarbamic acid 1-methylethyl ester; N-Phenyl isopropyl carbamate; Premalox; Profam; Propham; Triherbide; Triherbide-IPC; Tuberit; Tuberite CAS Registry Number: 122-42-9
2250
Propham
RTECS® Number: ED9100000 UN/NA & ERG Number: UN2757/151 EC Number: 204-542-0 Regulatory Authority and Advisory Bodies Carcinogenicity: IARC: Animal Inadequate Evidence; Human No Available Data, not classifiable as carcinogenic to humans, Group 3, 1987. Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. US EPA Hazardous Waste Number (RCRA No.): U363. Superfund/EPCRA [40CFR 302 and 355, F R: 8/16/06, Vol 71, No. 158] Reportable Quantity (RQ): 1000 lb (454 kg). RCRA, 40CFR261, Appendix 8 Hazardous Constituents. Reportable Quantity (RQ): 1 lb (0.454 kg). European/International Regulations: not listed in Annex 1. WGK (German Aquatic Hazard Class): No value assigned. Description: Propham is a colorless crystalline solid. Molecular weight 5 179.24; Freezing/Melting point 5 8788 C; 84 C (technical grade). Decomposition temperature 5 150 C. Insoluble in water. Potential Exposure: Those involved in the manufacture, formulation, and application of this grass-control herbicide. Permissible Exposure Limits in Air: Russia[43] set a MAC of 2.0 mg/m3 in work-place air and a MAC of 0.02 mg/m3 in ambient air of residential areas both on a momentary and a daily average basis. Permissible Concentration in Water: Russia[43] set a MAC of 0.2 mg/L in water bodies used for domestic purposes. The EPA has set a lifetime health advisory of 0.12 mg/L. Determination in Water: Analysis of propham is by a highperformance liquid chromatographic (HPLC) method applicable to the determination of certain carbamate and urea pesticides in water samples. This method requires a solvent extraction of approximately 1 L of sample with methylene chloride using a separatory funnel. The methylene chloride extract dried and concentrated to a volume of 10 mL or less. Compounds are separated by HPLC, and measurement is conducted with a UV detector. The method detection limit has not been determined for propham, but it is estimated that the detection limits for analytes included in this method are in the range of 15 μg/L. Fish Tox 5 5112.55273000 ppb (VERY LOW). Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Doses of 2000 mg/kg to rats produced loss of righting reflex, ptosis, piloerection, decreased locomotor activity, chronic pulmonary disease, rugation and irregular thickening of the stomach. The acute oral LD50 values in male and female rats were reported to be 3000 6 232 mg/kg and 2360 6 118 mg/kg, respectively. Carbamates are cholinesterase inhibitors. Symptoms of exposure include headache, giddiness, blurred vision, nervousness, weakness, nausea, cramps, diarrhea, and discomfort in the chest. Signs include sweating, tearing,
salivation, vomiting, cyanosis, convulsions, coma, loss of reflexes, and loss of sphincter control. Long Term Exposure: Cholinesterase inhibitor; cumulative effect is possible. This chemical may damage the nervous system with repeated exposure, resulting in convulsions, respiratory failure. May cause liver damage. Human Tox 5 100.00000 ppb (VERY LOW). Points of Attack: Respiratory system, lungs, central nervous system, cardiovascular system, skin, eyes, plasma and red blood cell cholinesterase. Medical Surveillance: Before employment and at regular times after that, the following are recommended: plasma and red blood cell cholinesterase levels (tests for the enzyme poisoned by this chemical). If exposure stops, plasma levels return to normal in 12 weeks while red blood cell levels may be reduced for 13 months. When cholinesterase enzyme levels are reduced by 25% or more below preemployment levels, risk of poisoning is increased, even if results are in lower ranges of “normal.” Reassignment to work not involving carbamate pesticides is recommended until enzyme levels recover. If symptoms develop or overexposure occurs, repeat the above tests as soon as possible and get an examination of the nervous system. Also, consider complete blood count. Consider chest X-ray following acute overexposure. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Speed in removing material from skin is of extreme importance. Shampoo hair promptly if contaminated. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a
β-Propiolactone full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, wellventilated area away from strong oxidizers. Where possible, automatically transfer material from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of this chemical should be grounded and bonded. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: Carbamate pesticides, solid, toxic, requires a shipping label of “POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 6.1 and Packing Group III. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Soil Adsorption Index (Koc) 5 200 (estimate). Fire Extinguishing: This chemical is a combustible solid. Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Poisonous gases are produced in fire, including nitrogen oxides. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant ($100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. In
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accordance with 40CFR165, follow recommendations for the disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by contacting your local or federal environmental control agency or by contacting your regional EPA office. Reference US Environmental Protection Agency. (August 1987). Health Advisory: Propham. Washington, DC: Office of Drinking Water
β-Propiolactone
P:1130
Molecular Formula: C3H4O2 Synonyms: Betaprone; BPL; Hydracrylic acid, β-lactone; 3Hydroxypropionic acid lactone; NSC21626; 2-Oxetanone; Propanoic acid, 3-hydroxy-, β-lactone; 3-Propanolide; Propanolide; 1,3-Propiolactone; 3-Propiolactone; Propiolactone; β-Propionolactone; Propionolactone, b CAS Registry Number: 57-57-8 RTECS® Number: RQ7350000 UN/NA & ERG Number: UN2810/153 EC Number: 200-340-1[Annex I Index No.: 606-031-00-1] Regulatory Authority and Advisory Bodies Carcinogenicity: NTP: 11th Report on Carcinogens, 2004: Reasonably anticipated to be a human carcinogen; IARC: Human No Adequate Data, Animal Sufficient Evidence, possibly carcinogenic to humans, Group 2B, 1999; NIOSH: Potential occupational carcinogen; OSHA: Potential human carcinogen. US EPA Gene-Tox Program, Positive: Carcinogenicity— mouse/rat; SHE—focus assay; Positive: Cell transform.— SA7/SHE; Positive: D. melanogaster—reciprocal translocation; Positive: Host-mediated assay; L5178Y cells In vitro—TK test; Positive: N. crassa—forward mutation; N. crassa—reversion; Positive: E. coli polA without S9; Histidine reversion—Ames test; Positive: D. melanogaster sex-linked lethal; Positive: In vitro UDS—human fibroblast; Positive: S. cerevisiae gene conversion; S. cerevisiae— homozygosis; Positive: S. cerevisiae—reversion; Positive/ dose response: In vitro SCE—nonhuman; Negative: Sperm morphology—mouse; Inconclusive: Mammalian micronucleus; Positive: CHO gene mutation. OSHA, 29CFR1910 Specifically Regulated Chemicals (See CFR 1910.1013). Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Clean Air Act: Hazardous Air Pollutants (Title I, Part A, Section 112). Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 500 lb (227 kg). Reportable Quantity (RQ): 10 lb (4.54 kg). EPCRA Section 313 Form R de minimis concentration reporting level: 0.1%. California Proposition 65 Chemical: Cancer 1/1/88.
2252
β-Propiolactone
European/International Regulations: Hazard Symbol: T1; Risk phrases: R45; R26; R36/38; Safety phrases: S53; S45. (see Appendix 4). WGK (German Aquatic Hazard Class): No value assigned. Description: β-Propiolactone is a colorless liquid which slowly hydrolyzes to hydracrylic acid and must be cooled to remain stable. Molecular weight 5 72.07; Specific gravity (H2O:1) 5 1.15 at 25 C; Boiling point 5 (decomposes) 161.7 C; Freezing/Melting point 5 33.3 C; Vapor pressure 5 3 mmHg at 25 C; Flash point 5 75 C. Explosive limits: LEL 5 2.9%; UEL—unknown. Hazard Identification (based on NFPA-704 M Rating System): Health 0, Flammability 2, Reactivity 0. Soluble in water; solubility 5 37%. Potential Exposure: Compound Description: Agricultural Chemical; Tumorigen, Mutagen. β-Propiolactone is used as a chemical intermediate in synthesis of acrylic acid and esters, acrylate plastics; as a vapor sterilizing agent; phase disinfectant; and a viricidal agent. Incompatibilities: Acetates, halogens, thiocyanates, thiosulfates, strong oxidizers, strong bases. May polymerize upon storage or due to warming. Stable if kept under refrigeration at 4050 F/510 C. Permissible Exposure Limits in Air OSHA PEL: Cancer suspect agent. Exposures of workers to this chemical is to be controlled through the required use of engineering controls, work practices, and personal protective equipment, including respirators. See 29CFR 1910.1003-1910.1016 for specific details of these requirements. NIOSH REL: A potential occupational carcinogen. [skin]; Limit exposure to lowest feasible concentration. See NIOSH Pocket Guide, Appendix A. ACGIH TLV®[1]: 0.5 ppm/1.5 mg/m3 TWA; confirmed animal carcinogen with unknown relevance to humans. NIOSH IDLH: Not determined. Potential occupational carcinogen. Protective Action Criteria (PAC) TEEL-0: 0.5 ppm PAC-1: 0.509 ppm PAC-2: 5.09 ppm PAC-3: 150 ppm DFG MAK: [skin] Carcinogen Category 2. Australia: TWA 0.5 ppm (1.5 mg/m3), carcinogen, 1993; Austria: carcinogen, 1999; Belgium: TWA 0.5 ppm (1.5 mg/m3), carcinogen, 1993; Denmark: TWA 0.1 ppm (1.5 mg/m3), 1999; Finland: carcinogen, 1999; France: carcinogen, 1993; Poland: MAC (TWA) 1 mg/m3, 1999; Sweden: carcinogen, 1999; Switzerland: MAK-W 0.5 ppm (1.5 mg/m3), carcinogen, 1999; United Kingdom: carcinogen, 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: confirmed animal carcinogen with unknown relevance to humans. Several states have set guidelines or standards for propiolactone in ambient air[60] ranging from zero (North Dakota) to 5.0 μg/m3 (New York) to 7.5 μg/m3 (South
Carolina) to 15 μg/m3 (Florida and Virginia) to 22.5 μg/m3 (Connecticut) to 36.0 μg/m3 (Nevada). Routes of Entry: Inhalation, ingestion, skin absorption, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Corrosive to the eyes. May cause corneal opacity and blindness. Irritates the respiratory tract. Contact with skin causes irritation, burns, and blistering; fluid from blisters may cause additional blistering of adjacent skin. Ingestion causes burns of mouth and stomach. The toxicity potential of this material via inhalation or ingestion is high; may cause death or permanent injury after very short exposures to small quantities. Long Term Exposure: A potential occupational carcinogen. May cause frequent urination, dysuria, hematuria (blood in the urine). May affect the liver and kidneys. Points of Attack: Kidneys, skin, lungs, eyes, liver. Cancer site in animals: liver, skin, and stomach. Medical Surveillance: Based on its high toxicity and carcinogenic effects in animals, preplacement and periodic examinations should include a history of exposure to other carcinogens, alcohol and smoking habits, medication, and family history. The skin, eye, lung, liver, and kidney should be evaluated. Sputum cytology may be helpful in evaluating the presence or absence of carcinogenic effects. Kidney and liver function tests. Periodic lung function tests. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. Butyl rubber is among the recommended protective materials. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Specific engineering controls are required for this chemical. Refer to OSHA Standard: beta-Propiolactone, 29 CFR 1910.1013. Respirator Selection: Employees engaged in handling operations involving this chemical must be provided with,
Propionaldehyde and required to wear and use, a half-mask filter-type respirator for dusts, mists, and fumes. A respirator affording higher levels of protection than this respirator may be substituted. At any detectable concentration: SCBAF: Pd, Pp (APF 5 10,000) (any NIOSH/MSHA- or European Standard EN 149-approved self-contained breathing apparatus that has a full face-piece and is operated in a pressuredemand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary, self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: GmFOv (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or back-mounted organic vapor canister] or SCBAE (any appropriate escapetype, self-contained breathing apparatus). Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Before entering confined space where this chemical may be present, check to make sure that an explosive concentration is not a danger. Store in a refrigerator or a freezer in glass containers and protect from air and light. Where possible, automatically pump liquid from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of 5 gallons or more of this chemical should be grounded and bonded. Drums must be equipped with self-closing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. A regulated, marked area should be established where this chemical is handled, used, or stored in compliance with OSHA Standard 1910.1045. Shipping: Toxic liquids, organic, n.o.s. require a label of “POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 6.1 and Packing Group I. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Establish forced ventilation to keep levels below explosive limit. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be
2253
properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible liquid. Poisonous gases are produced in fire. Use dry chemical, carbon dioxide, or alcohol foam extinguishers. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Dissolve or mix the material with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber. All federal, state, and local environmental regulations must be observed. References Sax, N. I. (Ed.). (1983). Dangerous Properties of Industrial Materials Report, 3, No. 2, 5760 US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Propiolactone, Beta-. Washington, DC: Chemical Emergency Preparedness Program New Jersey Department of Health and Senior Services. (August 2002). Hazardous Substances Fact Sheet: BetaPropiolactone. Trenton, NJ
Propionaldehyde
P:1140
Molecular Formula: C3H6O Common Formula: CH3CH2COH Synonyms: Aldehyde propionique (French); Methylacetaldehyde; NCI-C61029; Propaldehyde; Propanal; n-Propanal; 1-Propanal; Propanaldehyde; 1-Propanone; Propional; Propionic aldehyde; Propyl aldehyde; Propylic aldehyde CAS Registry Number: 123-38-6 RTECS® Number: UE0350000 UN/NA & ERG Number: UN1275/129 EC Number: 204-623-0 [Annex I Index No.: 605-018-00-8] Regulatory Authority and Advisory Bodies Carcinogenicity: EPA: Inadequate Information to assess carcinogenic potential.
2254
Propionaldehyde
Clean Air Act: Hazardous Air Pollutants (Title I, Part A, Section 112). Reportable Quantity (RQ): 1 lb (0.454 kg). EPCRA Section 313 Form R de minimis concentration reporting level: 1.0%. European/International Regulations: Hazard Symbol: F, Xi; Risk phrases: R11; R36/37/38; Safety phrases: S2; S9; S16; S29 (see Appendix 4). WGK (German Aquatic Hazard Class): 1—Low hazard to waters. Description: Propionaldehyde is a colorless liquid with a strong fruity odor. Molecular weight 5 58.09; Boiling point 5 49 C; Freezing/Melting point 5 81 C; Flash point 5 30 C; 29 C (oc); Autoignition temperature 5 207 C. Explosive limits: LEL 5 2.6%; UEL 5 17%. Hazard Identification (based on NFPA-704 M Rating System): Health 2, Flammability 3, Reactivity 2. Slightly soluble in water. Potential Exposure: Compound Description: Mutagen, Primary Irritant. Used as a synthetic flavoring; as a disinfectant and preservative; to make propionic acid; in plastic and rubber manufacturing; to make alkyl resins and plasticizers. Incompatibilities: Incompatible with strong acids, amines. Violent reaction with strong oxidizers. Strong caustics; reducing agents can cause explosive polymerization. Can self-ignite if finely dispersed on porous or combustible material, such as fabric. Heat or ultraviolet light can cause decomposition. Permissible Exposure Limits in Air AIHA WEEL: 20 ppm TWA. ACGIH TLV®[1]: 20 ppm/48 mg/m3 TWA. Protective Action Criteria (PAC)* TEEL-0: 20 ppm PAC-1: 45 ppm PAC-2: 260 ppm PAC-3: 840 ppm *AEGLs (Acute Emergency Guideline Levels) & ERPGs (Emergency Response Planning Guideline) are in bold face. Determination in Air: NIOSH Analytical Method #2539, aldehydes, screening. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Irritates the skin causing a burning sensation and rash on contact. Inhalation can irritate the respiratory tract and may cause nosebleeds, sore throat, cough, and phlegm. Higher exposures can cause pulmonary edema, a medical emergency that can be delayed for several hours. This can cause death. Long Term Exposure: Can irritate the lungs; bronchitis may develop. Testing has not been completed to determine the carcinogenicity of propionaldehyde. However, the limited studies to date indicate that these substances have chemical reactivity and mutagenicity similar to acetaldehyde and malonaldehyde. Therefore, NIOSH recommends that careful consideration should be given to reducing
exposures to this aldehyde. Further information can be found in the NIOSH Current Intelligence Bulletin 55: Carcinogenicity of Acetaldehyde and Malonaldehyde, and Mutagenicity of Related Low-Molecular-Weight Aldehydes [DHHS (NIOSH), Publication No. 91-112]. Points of Attack: Lungs, skin. Medical Surveillance: Lung function test. Consider chest X-ray following acute overexposure. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—Red: Flammability Hazard: Store in a flammable liquid storage area or approved cabinet away from ignition sources and corrosive and reactive materials. Prior to working with this chemical you should be trained on its proper handling and storage. Before entering confined space where this chemical may be present, check to make sure that an explosive concentration does not exist. Store in tightly closed containers in a cool, well-ventilated area away from oxidizers. Where possible, automatically pump
Propionic acid liquid from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of 5 gallons or more of this chemical should be grounded and bonded. Drums must be equipped with self-closing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosionproof electrical equipment and fittings. Shipping: Propionaldehyde requires a label of “FLAMMABLE LIQUID.” It falls in Hazard Class 3 and Packing Group II. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Establish forced ventilation to keep levels below explosive limit. Ventilate area of spill or leak. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible liquid. Poisonous gases are produced in fire. Do not use water. Use dry chemical, carbon dioxide extinguishers. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Reference New Jersey Department of Health and Senior Services. (May 2006). Hazardous Substances Fact Sheet: Propionaldehyde. Trenton, NJ
Propionic acid
2255
P:1150
Molecular Formula: C3H6O2 Common Formula: CH3CH2COOH Synonyms: Acide propionique (French); Carbonyethane; Carboxyethane; Ethanecarboxylic acid; Ethylformic acid; Metacetonic acid; Methylacetic acid; Propanoic acid; Propionic acid Grain preserver; Prozoin; Pseudoacetic acid; Sentry grain preserver; Tenox P grain preservative CAS Registry Number: 79-09-4 RTECS® Number: UE5950000 UN/NA & ERG Number: UN1848/132 EC Number: 201-176-3 [Annex I Index No.: 607-089-00-0] Regulatory Authority and Advisory Bodies Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. US EPA, FIFRA 1998 Status of Pesticides: Pesticide subject to registration or re-registration. FDA—over-the-counter drug. Clean Water Act: Section 311 Hazardous Substances/RQ 40CFR117.3 (same as CERCLA, see below). Reportable Quantity (RQ): 5000 lb (2270 kg). Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: Hazard Symbol: C; Risk phrases: R34; Safety phrases: S1/2; S23; S36; S45 (see Appendix 4). WGK (German Aquatic Hazard Class): 1—Low hazard to waters. Description: Propionic acid is a colorless liquid with a pungent odor. The odor threshold is 0.16 ppm. Molecular weight 5 74.09; Specific gravity (H2O:1) 5 0.99 at 25 C; Boiling point 5 141 C; Freezing/Melting point 5 21 C; Vapor pressure 5 3 mmHg at 25 C; Flash point 5 52.2 C (cc); 57 C (oc); Autoignition temperature 5 465 C. Explosive limits: LEL 5 2.9%; UEL 5 12.1%.[17] Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 2, Reactivity 1. Soluble in water. Potential Exposure: Compound Description: Agricultural Chemical; Mutagen, Primary Irritant. Propionic acid is used in the manufacture of inorganic propionates and propionate esters which are used as mold inhibitors, electroplating additives, emulsifying agents, flavors, and perfumes. It is an intermediate in pesticide manufacture, pharmaceutic manufacture; and in the production of cellulose propionate plastics. Also, used as grain preservative. Incompatibilities: The substance is a medium strong acid. Incompatible with sulfuric acid, strong bases, ammonia, isocyanates, alkylene oxides, epichlorohydrin. Reacts with bases, strong oxidizers, and amines, causing fire and explosion hazard. Attacks many metals forming flammable/ explosive hydrogen gas. Permissible Exposure Limits in Air Conversion factor: 1 ppm 5 3.03 mg/m3 at 25 C & 1 atm. OSHA PEL: None.
2256
Propionic acid
NIOSH REL: 10 ppm/30 mg/m3 TWA; 15 ppm/45 mg/m3 STEL. ACGIH TLV®[1]: 10 ppm/30 mg/m3 TWA. Protective Action Criteria (PAC) TEEL-0: 10 ppm PAC-1: 15 ppm PAC-2: 15 ppm PAC-3: 350 ppm DFG MAK: 10 ppm/31 mg/m3 TWA; Peak Limitation Category I(2); [skin]; Pregnancy Risk Group C. Australia: TWA 10 ppm (30 mg/m3); STEL 15 ppm, 1993; Austria: MAK 10 ppm (30 mg/m3), 1999; Belgium: TWA 10 ppm (30 mg/m3); STEL 15 ppm, 1993; Denmark: TWA 10 ppm (30 mg/m3), 1999; Finland: TWA 10 ppm, [skin], 1999; France: VME 10 ppm (30 mg/m3), 1999; the Netherlands: MAC-TGG 31 mg/m3, 2003; Russia: STEL 20 mg/m3, 1993; Sweden: NGV 10 ppm (30 mg/m3), KTV 15 ppm (45 mg/m3), 1999; Switzerland: MAK-W 10 ppm (30 mg/m3), KZG-W 20 ppm (60 mg/m3), 1999; United Kingdom: TWA 10 ppm (31 mg/m3); STEL 15 ppm (46 mg/m3), 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: TWA 10 ppm. Russia[43] set a MAC of 0.015 mg/m3 for ambient air in residential areas (15 μg/m3) on a momentary basis. Several states have set guidelines or standards for propionic acid in ambient air[60] ranging from 300450 μg/m3 (North Dakota) to 500 μg/m3 (Virginia) to 600 μg/m3 (Connecticut) to 714 μg/m3 (Nevada). Determination in Air: No method available. Determination in Water: Octanolwater coefficient: Log Kow 5 0.31. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Corrosive to the eyes, skin, and respiratory tract. Contact can cause severe eye burns, leading to permanent damage. Skin contact causes skin burns. Inhalation can cause irritation of the respiratory tract with mild cough; asthmatic response was found in medical reports of acute exposure of workers. Long Term Exposure: May cause an asthma-like allergy. May irritate the lungs; may lead to lung damage. Points of Attack: Skin, eyes, respiratory system. Medical Surveillance: For those with frequent or potentially high exposure (half the TLV or greater), the following are recommended before beginning work and at regular times after that: lung function tests. These may be normal if person is not having an attack at the time of the test. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions,
including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. If victim is conscious, administer water or milk. Do not induce vomiting. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. ACGIH recommends Neoprene™, nitrile rubber and polyvinyl chloride as protective materials. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Where there is potential for exposures over 10 ppm, use a NIOSH/MSHA- or European Standard EN149-approved full face-piece powered air-purifying respirators. Where there is potential for high exposures, use a NIOSH/MSHA- or European Standard EN149-approved supplied air-purifying respirators. Where there is potential for high exposures, use a NIOSH/MSHA- or European Standard EN149-approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuous-flow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—White: Corrosive or Contact Hazard; Store separately in a corrosion-resistant location. Prior to working with this chemical you should be trained on its proper handling and storage. Before entering confined space where this chemical may be present, check to make sure that an explosive concentration is not a danger. Store in containers made of aluminum or stainless steel. Propionic acid will corrode steel. Store in tightly closed containers in a cool, well-ventilated area away from oxidizers (such as perchlorates, peroxides, permanganates, chlorates, and nitrates), ignition sources, or heat. Outside or detached storage is preferred. Where possible, automatically pump liquid from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of 5 gallons or more of this chemical should be grounded and bonded. Drums must be equipped with self-closing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings.
Propionic anhydride Shipping: This compound requires a shipping label of “CORROSIVE.” It falls in Hazard Class 8 and Packing Group III. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Establish forced ventilation to keep levels below explosive limit. Cover spilled material with soda ash or sodium bicarbonate. Mix and add water. Neutralize and drain to sewer with plenty of water. Use water spray to dilute spill and disperse vapor. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a flammable liquid. Poisonous gases are produced in fire. Use dry chemical, carbon dioxide, or alcohol foam extinguishers. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Incineration in admixture with flammable solvent. Reference New Jersey Department of Health and Senior Services. (April 2001). Hazardous Substances Fact Sheet: Propionic Acid. Trenton, NJ
Propionic anhydride
P:1160
Molecular Formula: C6H10O3 Synonyms: Methylacetic anhydride; Propanoic anhydride; Propionic acid anhydride; Propionyl oxide
2257
CAS Registry Number: 123-62-6 RTECS® Number: UF9100000 UN/NA & ERG Number: UN2496/156 EC Number: 204-638-2 [Annex I Index No.: 607-010-00-X] Regulatory Authority and Advisory Bodies Clean Water Act: Section 311 Hazardous Substances/RQ 40CFR117.3 (same as CERCLA, see below). Reportable Quantity (RQ): 5000 lb (2270 kg). European/International Regulations: Hazard Symbol: C; Risk phrases: R34; Safety phrases: S1/2; S26; S45 (see Appendix 4). WGK (German Aquatic Hazard Class): 1—Low hazard to waters. Description: Propionic anhydride is a colorless liquid with a strong unpleasant odor. Molecular weight 5 130.16; Boiling point 5 167169 C; Freezing/Melting point 5 45 C; Flash point 5 63 C; Autoignition temperature 5 285 C. Explosive limits: LEL 5 1.3%; UEL 5 9.5%. Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 2, Reactivity 1. Decomposes in water. Potential Exposure: Used in the manufacture of perfumes, flavorings, alkyd resins; dyestuffs, pharmaceuticals; as an esterifying agent for fats, oils, and cellulose; dehydrating medium for nitrations and sulfonations. Incompatibilities: Oxidizers, strong acids, strong bases, reducing agents, alcohols, and metals. Contact water forms propionic acid. Permissible Exposure Limits in Air Protective Action Criteria (PAC) TEEL-0: 10 mg/m3 PAC-1: 30 mg/m3 PAC-2: 200 mg/m3 PAC-3: 500 mg/m3 Permissible Concentration in Water: High concentrations are dangerous to aquatic life. May be dangerous if it enters water intakes. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Irritates the eyes, skin, and respiratory tract. Eye contact can cause burns and permanent damage. Contact with liquid causes burns of skin. Ingestion causes burns of the mouth and stomach. High exposures can cause pulmonary edema, a medical emergency that can be delayed for several hours. This can cause death. Long Term Exposure: May cause skin allergy. Can irritate the lungs; bronchitis may develop. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions,
2258
Propionitrile
including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. If victim is conscious, administer water or milk. Do not induce vomiting. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—White: Corrosive or Contact Hazard; Store separately in a corrosion-resistant location. Prior to working with this chemical you should be trained on its proper handling and storage. Before entering confined space where this chemical may be present, check to make sure that an explosive concentration does not exist. Store in tightly closed containers in a cool, well-ventilated area away from oxidizers. Where possible, automatically pump liquid from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of 5 gallons or more of this chemical should be grounded and bonded. Drums must be equipped with self-closing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosionproof electrical equipment and fittings. Shipping: Propionic anhydride requires a shipping label of “CORROSIVE” It falls in Hazard Class 8 and Packing Group III. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Establish forced
ventilation to keep levels below explosive limit. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible liquid. Poisonous gases are produced in fire. Use dry chemical, carbon dioxide, or polymer alcohol foam extinguishers. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Incinerator with afterburner. Reference New Jersey Department of Health and Senior Services. (July 1999). Hazardous Substances Fact Sheet: Propionic Anhydride. Trenton, NJ
Propionitrile
P:1170
Molecular Formula: C3H5N Common Formula: CH3CH2CN Synonyms: Cianuro de etilo (Spanish); Cyanoethane; Ether cyanatus; Ethyl cyanide; Hydrocyanic ether; Propanenitrile; Propionic nitrile propylnitrile CAS Registry Number: 107-12-0 RTECS® Number: UF9625000 UN/NA & ERG Number: UN2404/131 EC Number: 203-464-4 Regulatory Authority and Advisory Bodies Department of Homeland Security Screening Threshold Quantity (pounds): Release hazard 10,000 ($1.00% concentration).
Propionitrile Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Clean Air Act: Accidental Release Prevention/Flammable Substances, (Section 112[r], Table 3), TQ 5 10,000 lb (4540 kg). US EPA Hazardous Waste Number (RCRA No.): P101. RCRA, 40CFR261, Appendix 8 Hazardous Constituents. RCRA 40CFR264, Appendix 9; TSD Facilities Ground. Water Monitoring List. Suggested test method(s) (PQL μg/L): 8015 (60); 8240 (5). Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 500 lb (227 kg). Reportable Quantity (RQ): 10 lb (4.54 kg). Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: not listed in Annex 1. WGK (German Aquatic Hazard Class): 1—Low hazard to waters. Description: Propionitrile is a colorless liquid with a pleasant, sweetish, ethereal odor. Molecular weight 5 55.09; Specific gravity (H2O:1) 5 0.78 at 25 C; Boiling point 5 97.2 C; Freezing/Melting point 5 2 91.7 C; Flash point 5 2.2 C (cc). Explosive limits: LEL 5 3.1%; UEL— unknown. Hazard Identification (based on NFPA-704 M Rating System): Health 4, Flammability 3, Reactivity 1. Soluble in water; solubility 5 12%. Potential Exposure: Compound Description: Mutagen; Reproductive Effector; Primary Irritant. Used as a solvent in petroleum refining, as a chemical intermediate, a raw material for drug manufacture, and a setting agent. Incompatibilities: Strong oxidizers and reducing agents; strong acids and bases. Hydrogen cyanide is produced when propionitrile is heated to decomposition. Reacts with acids, steam, warm water, producing toxic and flammable hydrogen cyanide fumes. Permissible Exposure Limits in Air Conversion factor: 1 ppm 5 2.25 mg/m3 at 25 C & 1 atm. OSHA PEL: None. NIOSH REL: TWA 6 ppm/14 mg/m3. ACGIH TLV®[1]: None. Protective Action Criteria (PAC)* TEEL-0: 6 ppm PAC-1: 6 ppm PAC-2: 7 ppm PAC-3: 37 ppm Determination in Air: Use NIOSH Analytical Method (IV). *AEGLs (Acute Emergency Guideline Levels) & ERPGs (Emergency Response Planning Guideline) are in bold face. #1606. Routes of Entry: Inhalation, skin absorption, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Contact may cause burns to skin and eyes. May affect the iron metabolism, causing asphyxia. It is highly toxic. Forms cyanide in the body. This super toxic compound has a probable oral lethal dose in humans
2259
of less than 5 mg/kg or a taste (less than 7 drops) for a 70kg (150 lb) person. Exposure results in headache, dizziness, rapid pulse, deep, rapid breathing, nausea, vomiting, unconsciousness, convulsions, and possible death. May cause cyanosis (blue coloration of skin and lips caused by lack of oxygen). Long Term Exposure: Chronic exposure over long periods may cause fatigue and weakness. Can cause same general symptoms as hydrogen cyanide but onset of symptoms is likely to be slower. May cause liver and kidney damage. Points of Attack: In animals: liver, kidney damage. Medical Surveillance: Liver and kidney function tests. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Use amyl nitrate capsules if symptoms develop. All area employees should be trained regularly in emergency measures for cyanide poisoning and in CPR. A cyanide antidote kit should be kept in the immediate work area and must be rapidly available. Kit ingredients should be replaced every 12 years to ensure freshness. Persons trained in the use of this kit, oxygen use, and CPR must be quickly available. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. For engineering controls, see NIOSH Criteria Document 212 Nitriles. Respirator Selection: 60 ppm: CcrOv (APF 5 10) [any chemical cartridge respirator with organic vapor cartridge (s)] or Sa (APF 5 10) (any supplied-air respirator). 150 ppm: Sa:Cf (APF 5 25) (any supplied-air respirator operated in a continuous-flow mode) or PaprOv (APF 5 25) [any powered, air-purifying respirator with organic vapor cartridge(s)]. 300 ppm: CcrFOv (APF 5 50) [any airpurifying, full-face-piece respirator (gas mask) with a chinstyle, front- or back-mounted acid gas canister] or GmFOv (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or back-mounted acid gas canister] or PaprTOv (APF 5 50) [any powered, airpurifying respirator with a tight-fitting face-piece and
2260
Propoxur
organic vapor cartridge(s)] or SCBAF (APF 5 50) (any selfcontained breathing apparatus with a full face-piece) or SaF (APF 5 50) (any supplied-air respirator with a full facepiece). 1000 ppm: SaF: Pd,Pp (APF 5 2000) (any suppliedair respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd,Pp (APF 5 10,000) (any self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positivepressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: GmFOv (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or back-mounted organic vapor canister] or SCBAE (any appropriate escape-type, self-contained breathing apparatus). Storage: Color Code—Red: Flammability Hazard: Store in a flammable liquid storage area or approved cabinet away from ignition sources and corrosive and reactive materials. Prior to working with this chemical you should be trained on its proper handling and storage. Before entering confined space where this chemical may be present, check to make sure that an explosive concentration is not a danger. Store in an explosion-proof refrigerator. Where possible, automatically pump liquid from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of 5 gallons or more of this chemical should be grounded and bonded. Drums must be equipped with self-closing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: This compound requires a shipping label of ““FLAMMABLE LIQUID, POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 3 and Packing Group II. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Do not touch spilled material; stop leak if you can do it without risk. Use water spray to reduce vapors. Small spills: take up with sand or other noncombustible absorbent material and place into containers for later disposal. Large spills: dike far ahead of spill for later disposal. Establish forced ventilation to keep levels below explosive limit. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the
buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a flammable liquid. Poisonous gases, including hydrogen cyanide, are produced in fire. Use dry chemical, carbon dioxide, or alcohol foam extinguishers. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Alcoholic NaOH followed by calcium hypochlorite may be used. Incineration is also recommended.[22] Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant ($100 kg/ mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. References US Environmental Protection Agency. (September 2, 1983). Chemical Hazard Information Profile Draft Report: Propionitrile. Washington, DC US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Propionitrile. Washington, DC: Chemical Emergency Preparedness Program
Propoxur
P:1180
Molecular Formula: C11H15NO3 Synonyms: 58-12-315; Arprocarb; BAY39007; BAY 5122; Bayer 39007; Bayer B 5122; Baygon; Blattanex; Blattosep; Bolfo; Boruho; Boruho 50; Brygou; Carbamic acid, methyl-, o-isopropoxyphenyl ester; Dalf dust; ENT25,671; Invisi-gard; IPMC; o-(2-Isopropoxyphenyl) N-methylcarbamate; o-Isopropoxyphenyl N-methylcarbamate; oIsopropoxyphenyl methylcarbamate; 2-Isopropoxyphenyl
Propoxur N-methylcarbamate; 2-Isopropoxyphenyl methylcarbamate; 2-(1-Methylethoxy)phenyl N-methylcarbamate; OMS 33; PHC; Phenol, 2-(1-methylethoxy)-, methylcarbamate; Propotox; Propoxylor; Sendran; Suncide; Tendex; Unden CAS Registry Number: 114-26-1 RTECS® Number: FC3150000 UN/NA & ERG Number: UN2757/151 EC Number: 204-043-8 [Annex I Index No.: 006-16-00-4] Regulatory Authority and Advisory Bodies US EPA Gene-Tox Program, Negative: B. subtilis rec assay; TRP reversion; Negative: S. cerevisiae gene conversion; Inconclusive: B. subtilis rec assay. US EPA, FIFRA 1998 Status of Pesticides: RED completed. Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Clean Air Act: Hazardous Air Pollutants (Title I, Part A, Section 112). US EPA Hazardous Waste Number (RCRA No.): U411. RCRA, 40CFR261, Appendix 8 Hazardous Constituents. RCRA 40CFR268.48; 61FR15654, Universal Treatment Standards: Wastewater (mg/L), 0.056; Nonwastewater (mg/ kg), 1.4. Reportable Quantity (RQ): 1 lb (0.454 kg). EPCRA Section 313 Form R de minimis concentration reporting level: 1.0%. US DOT Regulated Marine Pollutant (49CFR172.101, Appendix B). California Proposition 65 Chemical: Cancer 8/11/06. European/International Regulations: Hazard Symbol: T, N; Risk phrases: R25; R50/53; Safety phrases: S1/2; S37; S45; S60; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): 3—Severe hazard to waters. Description: Propoxur is a colorless crystalline powder with a faint characteristic odor. Molecular weight 5 209.27; Boiling point 5 N/A (decomposes); Freezing/Melting point 5 91 C; Flash point $ 149 C. Hazard Identification (based on NFPA-704 M Rating System): Health 2, Flammability 1, Reactivity 0. Poor solubility in water. Potential Exposure: Compound Description: Agricultural Chemical; Mutagen; Reproductive Effector; Human Data. Personnel engaged in the manufacture, formulation, and application of this carbamate agricultural chemical and pesticide. Incompatibilities: Strong oxidizers, alkalis, heat, and moisture. Emits highly toxic methyl isocyanate fumes when heated to decomposition. Permissible Exposure Limits in Air OSHA PEL: None. NIOSH REL: 0.5 mg/m3 TWA. ACGIH TLV®[1]: 0.5 mg/m3 TWA; confirmed animal carcinogen with unknown relevance to humans. BEIA issued for Acetylcholinesterase-inhibiting pesticides. Protective Action Criteria (PAC) TEEL-0: 0.5 mg/m3
2261
PAC-1: 1.5 mg/m3 PAC-2: 2.5 mg/m3 PAC-3: 20 mg/m3 DFG MAK: 2 mg/m3 measured as the, inhalable fraction TWA; Peak Limitation Category II(8). Australia: TWA 0.5 mg/m3, 1993; Austria: MAK 0.5 mg/ m3, 1999; Belgium: TWA 0.5 mg/m3, 1993; Denmark: TWA 0.5 mg/m3, 1999; Finland: TWA 0.5 mg/m3; STEL 1.5 mg/m3, 1993; France: VME 0.5 mg/m3, 1999; the Netherlands: MAC-TGG 0.5 mg/m3, 2003; Poland: MAC (TWA) 0.5 mg/m3; MAC (STEL) 2 mg/m3, 1999; Switzerland: MAK-W 0.5 mg/m3, 1999; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: confirmed animal carcinogen with unknown relevance to humans. Several states have set guidelines or standards for Baygon in ambient air[60] ranging from 520 μg/m3 (North Dakota) to 8 μg/m3 (Virginia) to 10 μg/m3 (Connecticut) to 12 μg/m3 (Nevada). Determination in Air: No method available. Determination in Water: Fish Tox 5 168.01099000 MATC (LOW). Octanolwater coefficient: Log Kow 5 1.5. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Propoxur can affect you when breathed in and quickly enters the body by passing through the skin. Severe poisoning can occur from skin contact. It is a moderately toxic carbamate chemical. Exposure can cause severe carbamate poisoning, with symptoms of headaches, sweating, nausea and vomiting, diarrhea, muscle twitching, loss of coordination, and even death. May affect the nervous system, liver, kidneys. A cholinesterase inhibitor. Long Term Exposure: Propoxur may cause mutations. Handle with extreme caution. It may damage the developing fetus. Cholinesterase inhibitor; cumulative effect is possible. This chemical may damage the nervous system with repeated exposure, resulting in convulsions, respiratory failure. May cause liver damage. Human Tox 5 94.85095 ppb CHCL (Chronic Human Carcinogen Level) (LOW). Points of Attack: Central nervous system, liver, kidneys, gastrointestinal tract, blood cholinesterase. Medical Surveillance: If symptoms develop or overexposure is suspected, the following may be useful: serum and RBC cholinesterase levels (a test for the enzyme in the body affected by propoxur). These tests are useful only if done 12 hours after exposure and can return to normal before the person feels well. Before employment and at regular times after that, the following are recommended: plasma and red blood cell cholinesterase levels (tests for the enzyme poisoned by this chemical). If exposure stops, plasma levels return to normal in 12 weeks while red blood cell levels may be reduced for 13 months. When cholinesterase enzyme levels are reduced by 25% or more below preemployment levels, risk of poisoning is increased, even if results are in lower ranges of “normal.” Reassignment to work not involving carbamate pesticides is
2262
n-Propyl acetate
recommended until enzyme levels recover. If symptoms develop or overexposure occurs, repeat the above tests as soon as possible and get an examination of the nervous system. Also, consider complete blood count. Consider chest X-ray following acute overexposure. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Where there is potential for exposures over 0.5 mg/m3, use a NIOSH/MSHA- or European Standard EN149-approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuous-flow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, wellventilated area away from heat, moisture, oxidizers, alkaline environments. Where possible, automatically transfer material from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of this chemical should be grounded and bonded. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: Carbamate pesticides, solid, toxic, require a shipping label of “POISONOUS/TOXIC MATERIALS.” This material falls in DOT Hazard Class 6.1 and Packing Group III.
Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Soil Adsorption Index (Koc) 5 30. Fire Extinguishing: This chemical is a combustible solid. Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Highly toxic gases are produced in fire, including methyl isocyanate. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: In accordance with 40CFR165, follow recommendations for the disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by contacting your local or federal environmental control agency or by contacting your regional EPA office. Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant ($100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. Reference New Jersey Department of Health and Senior Services. (July 2005). Hazardous Substances Fact Sheet: Propoxur. Trenton, NJ
n-Propyl acetate
P:1190
Molecular Formula: C5H10O2 Common Formula: CH3COOCH2CH2CH3 Synonyms: Acetate de propyle normal (French); Acetic acid, propyl ester; Acetic acid, n-propyl ester; 1Acetoxypropane; Propyl acetate; n-Propyl acetate; 1-Propyl acetate; Propylacetate Isopropyl Acetate—see separate record
n-Propyl acetate CAS Registry Number: 109-60-4 RTECS® Number: AJ3675000 UN/NA & ERG Number: UN1276/129 EC Number: 203-686-1 [Annex I Index No.: 607-024-00-6] Regulatory Authority and Advisory Bodies Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: Hazard Symbol: F; Risk phrases: R1; R 36; R66; R67; Safety phrases: S2; S16; S26; S29; S33 (see Appendix 4). WGK (German Aquatic Hazard Class): 1—Low hazard to waters. Description: n-Propyl acetate is a colorless liquid with a mild, fruity odor. The odor threshold is 70 mg/m3[41] and 2.8 mg/m3 (New Jersey Fact Sheet). Molecular weight 5 102.15 (both isomers); Specific gravity (H2O:1) 5 0.84 at 25 C; Boiling point 5 101.7 C; Freezing/ Melting point 5 92.2 C; Vapor pressure 5 25 mmHg at 25 C; Flash point 5 13 C; Autoignition temperature 5 450 C. Explosive limits: LEL 5 1.7% at 38 C; UEL 5 8.0%. Hazard Identification (based on NFPA-704 M Rating System): Health 1, Flammability 3, Reactivity 0. Slightly soluble in water; solubility 5 2%. Potential Exposure: Compound Description (both isomers): Human Data; Primary Irritant. Propyl acetate is a used as a solvent for plastics and cellulose ester resins; perfume ingredient; component of food flavoring. It is also used as a chemical intermediate. Incompatibilities: Contact with nitrates, strong oxidizers, strong alkalis, strong acids; may pose risk of fire and explosions. Attacks plastic. Permissible Exposure Limits in Air Conversion factor: 1 ppm 5 4.18 mg/m3 at 25 C & 1 atm. OSHA PEL: 200 ppm/840 mg/m3 TWA. NIOSH REL: 200 ppm/840 mg/m3 TWA; 250 ppm/ 1050 mg/m3 STEL. ACGIH TLV®[1]: 200 ppm/835 mg/m3 TWA; 250 ppm/ 1040 mg/m3 STEL. NIOSH IDLH: 1700 ppm. Protective Action Criteria (PAC) TEEL-0: 200 ppm PAC-1: 250 ppm PAC-2: 250 ppm PAC-3: 1700 ppm DFG MAK: 100 ppm/420 mg/m3 TWA; Peak Limitation Category I(2); Pregnancy Risk Group D. Australia: TWA 200 ppm (840 mg/m3); STEL 250 ppm, 1993; Austria: MAK 200 ppm (840 mg/m3), 1999; Belgium: TWA 200 ppm (835 mg/m3); STEL 250 ppm (1040 mg/m3), 1993; Finland: TWA 200 ppm (840 mg/m3); STEL 250 ppm (1050 mg/m3), 1993; France: VME 200 ppm (840 mg/m3), 1999; Hungary: TWA 200 mg/m3; STEL 600 mg/m3, [skin], 1993; the Netherlands: MACTGG 420 mg/m3, 2003; Norway: TWA 100 ppm
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(420 mg/m3), 1999; the Philippines: TWA 200 ppm (840 mg/m3), 1993; Poland: MAC (TWA) 200 mg/m3; MAC (STEL) 1000 mg/m3, 1999; Russia: TWA 200 ppm; STEL 200 mg/m3, 1993; Switzerland: MAK-W 200 ppm (840 mg/m3), KZG-W 400 ppm, 1999; Turkey: TWA 200 ppm (840 mg/m3), 1993; United Kingdom: TWA 200 ppm (849 mg/m3); STEL 250 ppm (1060 mg/m3); Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: STEL 250 ppm. Several states have set guidelines or standards for propyl acetate in ambient air[60] ranging from 8.410.5 mg/m3 (North Dakota) to 14 mg/m3 (Virginia) to 16.8 mg/m3 (Connecticut) to 20 mg/m3 (Nevada). Determination in Air: Use NIOSH Analytical Method (IV) #1401, alcohols II; #1405, alcohols, Combined; OSHA Analytical Method 7, Organic Vapors. Determination in Water: Octanolwater coefficient: Log Kow 5 1.23. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: n-Propyl acetate can affect you when breathed in. Exposure can irritate the eyes, nose, and throat. Very high levels are narcotic and may affect the nervous system and cause you to feel dizzy, lightheaded, and to pass out. Long Term Exposure: Prolonged or repeated contact can cause drying and cracking of the skin. Points of Attack: Eyes, skin, respiratory system, central nervous system. Medical Surveillance: There is no special test for this substance. However, if illness occurs or overexposure is suspected, medical attention is recommended. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. Butyl rubber, polyvinyl alcohol, and Silvershield™ are recommended protective materials. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working
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Propyl alcohol
with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Up to 1700 ppm: Sa:Cf (APF 5 25) (any supplied-air respirator operated in a continuous-flow mode) or CcrFOv (APF 5 50) [any air-purifying, full-facepiece respirator (gas mask) with a chin-style, front- or back-mounted acid gas canister] or GmFOv (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or back-mounted organic vapor canister] or PaprOv (APF 5 25) [any powered, air-purifying respirator with organic vapor cartridge(s)] or SCBAF (APF 5 50) (any self-contained breathing apparatus with a full face-piece) or SaF (APF 5 50) (any supplied-air respirator with a full face-piece). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd,Pp (APF 5 10,000) (any self-contained breathing apparatus that has a full face-piece and is operated in a pressuredemand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: GmFOv (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or back-mounted organic vapor canister] or SCBAE (any appropriate escapetype, self-contained breathing apparatus). Storage: Color Code—Red: Flammability Hazard: Store in a flammable liquid storage area or approved cabinet away from ignition sources and corrosive and reactive materials. Prior to working with this chemical you should be trained on its proper handling and storage. Before entering confined space where this chemical may be present, check to make sure that an explosive concentration is not a danger. n-Propyl acetate must be stored to avoid contact with nitrates, strong oxidizers (such as chlorine, bromine, and fluorine), and strong acids (such as hydrochloric, sulfuric, and nitric) since violent reactions occur. Store in tightly closed containers in a cool, well-ventilated area away from heat. n-Propyl acetate will dissolve some plastics and resins. Sources of ignition, such as smoking and open flames, are prohibited where n-propyl acetate is handled, used, or stored. Metal containers involving the transfer of 5 gallons or more of n-propyl acetate should be grounded and bonded. Drums must be equipped with self-closing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of n-propyl acetate. Shipping: n-Propyl acetate requires a shipping label of “FLAMMABLE LIQUID.” It falls in Hazard Class 3 and Packing Group II. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup
is complete. Remove all ignition sources. Establish forced ventilation to keep levels below explosive limit. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a flammable liquid. Poisonous gases are produced in fire. Use dry chemical, carbon dioxide, or alcohol foam extinguishers. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Dissolve or mix the material with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber. All federal, state, and local environmental regulations must be observed. Reference New Jersey Department of Health and Senior Services. (March 2001). Hazardous Substances Fact Sheet: n-Propyl Acetate. Trenton, NJ
Propyl alcohol
P:1200
Molecular Formula: C3H8O (n-); C6H14O (iso-) Synonyms: Alcohol C-3; Alcool propylique (French); Ethyl carbinol; 1-Hydroxypropane; Optal; Osmosol extra; Propanol-1; 1-Propanol; n-Propanol; Propanole (German); Propyl alcohol; Propyl alcohol, normal; 1-Propyl alcohol; n-Propyl alkohol (German); Propylic alcohol
Propyl alcohol (iso-) 2-Methylpentan-1-ol CAS Registry Number: 71-23-8; 105-30-6 (iso-) RTECS® Number: UH8225000 (n-) UN/NA & ERG Number: UN1274 (n-propanol)/129 EC Number: 200-746-9 [Annex I Index No.: 603-003-00-0 (n-)]; 203-285-1 [2-methylpentan-1-ol] Regulatory Authority and Advisory Bodies US EPA Gene-Tox Program, Negative: In vitro SCE— nonhuman. US EPA, FIFRA 1998 Status of Pesticides: Canceled. Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: Hazard Symbol: F, Xi; Risk phrases: R11; R47; R67; Safety phrases: S2; S7; S16; S26; S39 (see Appendix 4). WGK (German Aquatic Hazard Class): 1—Low hazard to waters. Description: The two isomers of propyl alcohol are n-propyl alcohol and isopropyl alcohol. The odor threshold is 5.3 ppm[41] and 2.6 ppm (NJ). Both are colorless, volatile liquids. Isopropyl alcohol is discussed in a separate entry in this volume. n-Propanol: Molecular weight 5 60.11; Specific gravity (H2O:1) 5 0.81 at 25 C; Boiling point 5 97 C; Freezing/Melting point 5 127 C; Vapor pressure 5 15 mmHg at 25 C; Flash point 5 22.2 C; Autoignition temperature 5 412 C. Explosive limits: LEL 5 2.2%; UEL 5 13.7%. Hazard Identification (based on NFPA-704 M Rating System): Health 1, Flammability 3, Reactivity 0. Soluble in water. Potential Exposure: Compound Description (n-): Agricultural Chemical; Tumorigen, Mutagen; Reproductive Effector; Human Data; Primary Irritant. n-Propyl alcohol is used as a solvent in lacquers, dopes; to make cosmetics, dental lotions, cleaners, polishes, and pharmaceuticals; as a surgical antiseptic. It is a solvent for vegetable oils, natural gums and resins; rosin, shellac, certain synthetic resins; ethyl cellulose and butyral; as a degreasing agent; as a chemical intermediate. Incompatibilities: Strong oxidizers. Permissible Exposure Limits in Air OSHA PEL: 200 ppm/500 mg/m3 TWA. NIOSH REL: 200 ppm/500 mg/m3 TWA; 250 ppm/625 mg/ m3 STEL [skin]. ACGIH TLV®[1]: 100 ppm/246 mg/m3 TWA; Not Classifiable as a Human Carcinogen. NIOSH IDLH: 800 ppm. Protective Action Criteria (PAC) TEEL-0: 200 ppm PAC-1: 250 ppm PAC-2: 250 ppm PAC-3: 800 ppm isopropanol OSHA PEL: 400 ppm/980 mg/m3 TWA.
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NIOSH REL: 400 ppm/980 mg/m3 TWA; 500 ppm/ 1225 mg/m3 STEL ACGIH TLV®[1]: 200 ppm/492 mg/m3 TWA; 400 ppm/ 984 mg/m3 STEL, Not Classifiable as a Human Cardinogen; BEI issued. TEEL-0: 0.25 ppm PAC-1: 0.75 ppm PAC-2: 5 ppm PAC-3: 150 ppm DFG MAK: 200 ppm/500 mg/m3 [skin]; BAT: 50 mg [Acetone]/L in blood or urine/end-of-shift as isopropyl alcohol. Australia: TWA 200 ppm (500 mg/m3); 200 ppm (492 mg/ m3) STEL [skin], 1993; Austria: MAK 200 ppm (500 mg/ m3), 1999; Belgium: TWA 200 ppm (492 mg/m3); STEL 250 ppm, [skin], 1993; Denmark: TWA 200 ppm (500 mg/ m3), [skin], 1999; Finland: TWA 200 ppm (500 mg/m3); STEL 250 ppm, [skin], 1999; France: VME 200 ppm (500 mg/m3), 1999; Hungary: TWA 100 mg/m3; STEL 200 mg/m3, 1993; Norway: TWA 100 ppm (245 mg/m3), 1999; Poland: MAC (TWA) 200 mg/m3; MAC (STEL) 600 mg/m3, 1999; Russia: STEL 10 mg/m3, 1993; Sweden: NGV 150 ppm (350 mg/m3), KTV 250 ppm (600 mg/m3), 1999; Switzerland: MAK-W 200 ppm (500 mg/m3), [skin], 1999; Turkey: TWA 200 ppm (500 mg/m3), 1993; United Kingdom: TWA 200 ppm (500 mg/m3); STEL 250 ppm, [skin], 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: STEL 250 ppm [skin]. Russia[35, 43] set a MAC value of 0.3 mg/m3 for ambient air in residential areas[60] both on a momentary and a daily average basis. Several states have set guidelines or standards for propanol in ambient air[60] ranging from 0.67 mg/m3 (Massachusetts) to 5.06.25 mg/ m3 (North Dakota) to 8.0 mg/m3 (Virginia) to 10.0 mg/m3 (Connecticut) to 11.905 mg/m3 (Nevada). Determination in Air: Use NIOSH Analytical Method #1401, alcohols.[18] Permissible Concentration in Water: EPA[32] has suggested a permissible ambient goal of 6900 μg/L based on health effects. Russia[35, 43] set a MAC of 0.25 mg/L in water bodies used for domestic purposes. Routes of Entry: Inhalation of vapor, percutaneous absorption, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Propyl alcohol can affect you when breathed in and by passing through your skin. Irritates the eyes, skin, and respiratory tract. Prolonged skin contact can cause a burning sensation and rash. Exposure to high concentrations can affect the central nervous system and cause headaches, drowsiness, dizziness, and confusion; may cause ataxia, gastrointestinal pain, abdominal cramps, nausea, vomiting, diarrhea. High levels can cause unconsciousness. Long Term Exposure: Repeated skin exposure may cause drying and cracking of the skin. Propyl alcohol may cause mutations. Handle with extreme caution. This chemical is listed by the state of New Jersey as a Special Health Hazard
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Propyl alcohol
and a data sheet (listed below) states that this chemical may be a carcinogen in humans: It has been shown to cause liver carcinomas and sarcoma, spleen sarcoma, and leukemia in animals. It should be treated with caution. Points of Attack: Eyes, skin, respiratory system, gastrointestinal tract, central nervous system. May cause liver damage. It may cause brain or nerve damage. Medical Surveillance: Liver function tests. Evaluate for brain and nerve effects including cerebellar, autonomic and peripheral nervous systems, changes in memory, concentration, sleeping pattern, mood, headaches, and fatigue. Positive and borderline individuals should be referred for neuropsychological testing. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. Neoprene™, Teflon™, nitrile, and polyvinyl acetate are recommended protective materials. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full facepiece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Up to 800 ppm: CcrOv (APF 5 10) [any chemical cartridge respirator with organic vapor cartridge(s)] or PaprOv (APF 5 25) [any powered, air-purifying respirator with organic vapor cartridge(s)] or GmFOv (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chinstyle, front- or back-mounted organic vapor canister]; Sa (APF 5 10) (any supplied-air respirator) or SCBAF (APF 5 50) (any self-contained breathing apparatus with a full face-piece). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd,Pp (APF 5 10,000) (any self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary self-contained breathing apparatus operated in a pressure-demand or
other positive-pressure mode). Escape: GmFOv (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or back-mounted organic vapor canister] or SCBAE (any appropriate escape-type, self-contained breathing apparatus). Note: Substance reported to cause eye irritation or damage; may require eye protection. Storage: Color Code—Red: Flammability Hazard: Store in a flammable liquid storage area or approved cabinet away from ignition sources and corrosive and reactive materials. Prior to working with this chemical you should be trained on its proper handling and storage. Before entering confined space where this chemical may be present, check to make sure that an explosive concentration is not a danger. Propyl alcohol must be stored to avoid contact with strong oxidizers (such as chlorine and bromine) since violent reactions occur. Store in tightly closed containers in a cool, wellventilated area away from heat. Sources of ignition, such as smoking and open flames, are prohibited where propyl alcohol is used, handled, or stored in a manner that could create a potential fire or explosion hazard. Metal containers involving the transfer of 5 gallons or more of propyl alcohol should be grounded and bonded. Drums must be equipped with self-closing valves, pressure vacuum bungs, and flame arresters. A regulated, marked area should be established where this chemical is handled, used, or stored in compliance with OSHA Standard 1910.1045. Shipping: This compound requires a shipping label of “FLAMMABLE LIQUID.” It falls in Hazard Class 3 and Packing Group II or III. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Establish forced ventilation to keep levels below explosive limit. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a flammable liquid. Poisonous gases are produced in fire. Use dry chemical, carbon dioxide, or alcohol foam extinguishers. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters
Propylamine waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Dissolve or mix the material with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber. All federal, state, and local environmental regulations must be observed. References US Environmental Protection Agency. (March 31, 1983). Chemical Hazard Information Profile Draft Report: nPropanol. Washington, DC New Jersey Department of Health and Senior Services. (June 2005). Hazardous Substances Fact Sheet: Propyl Alcohol. Trenton, NJ
Propylamine
P:1210
Molecular Formula: C3H9N Common Formula: CH3CH2CH2NH2 Synonyms: 1-Aminopropane; 1-Iodopropane; Mono-n-propylamine; Monopropylamine; Propanamine; n-Propilamina (Spanish); Propylamine CAS Registry Number: 107-10-8 RTECS® Number: UN9100000 UN/NA & ERG Number: UN1277/132 EC Number: 203-462-3 Regulatory Authority and Advisory Bodies Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. US EPA Hazardous Waste Number (RCRA No.): U194. RCRA, 40CFR261, Appendix 8 Hazardous Constituents. Reportable Quantity (RQ): 5000 lb (2270 kg). Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: not listed in Annex 1. WGK (German Aquatic Hazard Class): 1—Low hazard to waters. Description: n-Propylamine is a water-white liquid with a strong irritating odor similar to that of ammonia. Molecular weight 5 59.13; Specific gravity (H2O:1) 5 0.71 at 25 C; Boiling point 5 49 C; Freezing/Melting point 5 2 83 C; Flash point 5 , 2 37 C; Autoignition temperature 5 318 C. Explosive limits: LEL 5 2.0%; UEL 5 10.4%. Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 3, Reactivity 0. Soluble in water.
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Potential Exposure: Compound Description: Primary Irritant. Propylamine is used to make textile resins, drugs, pesticides, and other chemicals. Incompatibilities: Violent reaction with oxidizers and mercury, strong acids, organic anhydrides, isocyanates, aldehydes, nitroparaffins, halogenated hydrocarbons, alcohols, and many other compounds. Attacks many metals and alloys, especially copper. Aqueous solutions may attack glass. Permissible Exposure Limits in Air Protective Action Criteria (PAC) TEEL-0: 15 ppm PAC-1: 50 ppm PAC-2: 250 ppm PAC-3: 250 ppm Finland: STEL 5 ppm (12 mg/m3), [skin], 1999; Russia[43] set a MAC of 5 mg/m3 in work-place air. It should be recognized that propylamine can be absorbed through your skin, thereby increasing your exposure. Permissible Concentration in Water: Russia[43] set a MAC of 0.5 mg/L in water bodies used for domestic purposes. Determination in Water: Octanolwater coefficient: Log Kow 5 0.2. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Absorbed through the skin. Harmful Effects and Symptoms Short Term Exposure: Propylamine can affect you when breathed in and by passing through your skin. Corrosive to the eyes, skin, and respiratory tract. Propylamine can cause severe eye burns leading to permanent damage and blindness. Contact can cause severe skin burns. Breathing Propylamine can irritate the lungs, causing coughing and/or shortness of breath. Higher exposures can cause a buildup of fluid in the lungs (pulmonary edema). This can cause death. Overexposure may damage lungs, liver, kidneys, and heart muscle. Long Term Exposure: Repeated lower exposure may damage the lungs, liver, kidneys, and/or heart muscle. Some amines cause skin or lung sensitization and allergy; however, it is not known if this chemical causes these allergies. Points of Attack: Lungs, liver, kidneys, heart. Medical Surveillance: Before beginning employment and at regular times after that, the following are recommended: lung function tests. If symptoms develop or overexposure is suspected, the following may also be useful: tests for kidney and liver function. Consider chest X-ray after acute overexposure. Evaluation by a qualified allergist, including careful exposure history and special testing, may help diagnose skin allergy. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including
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Propyl chloroformate
resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. Teflon™ and polyvinyl acetate are among the recommended protective materials. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Where there is potential for exposure to propylamine, use a NIOSH/MSHA- or European Standard EN149-approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuous-flow mode; or use a MSHA/NOSH-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—Red: Flammability Hazard: Store in a flammable liquid storage area or approved cabinet away from ignition sources and corrosive and reactive materials. Prior to working with this chemical you should be trained on its proper handling and storage. Before entering confined space where this chemical may be present, check to make sure that an explosive concentration is not a danger. Propylamine is incompatible with strong acids (such as hydrochloric, sulfuric, and nitric), acid anhydrides, acid chlorides, strong oxidizers (such as chlorine, bromine, and fluorine), carbon dioxide, and triethynyl aluminum. Store in tightly closed containers in a cool, well-ventilated area away from oxidizers. Sources of ignition, such as smoking and open flames, are prohibited where Propylamine is used, handled, or stored in a manner that could create a potential fire or explosion hazard. Metal containers involving the transfer of 5 gallons or more of propylamine should be grounded and bonded. Drums must be equipped with selfclosing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of propylamine. Wherever propylamine is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: This compound requires a shipping label of “FLAMMABLE LIQUID, CORROSIVE.” It falls in Hazard Class 3 and Packing Group II.
Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Establish forced ventilation to keep levels below explosive limit. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a flammable liquid. Poisonous gases are produced in fire. Use dry chemical, carbon dioxide, or alcohol foam extinguishers. Water may be ineffective for fighting fires. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant ($100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. Reference New Jersey Department of Health and Senior Services. (March 2001). Hazardous Substances Fact Sheet: Propylamine. Trenton, NJ
Propyl chloroformate
P:1220
Molecular Formula: C4H7ClO2 Common Formula: ClCOOC3H7 Synonyms: Carbonochloridic acid, Propyl ester; Chloroformic acid propyl ester; Propyl chlorocarbonate; n-Propyl chloroformate
Propyl chloroformate CAS Registry Number: 109-61-5 RTECS® Number: LQ6830000 UN/NA & ERG Number: UN2740/155 EC Number: 203-687-7 [Annex I Index No.: 607-142-00-8] Regulatory Authority and Advisory Bodies Department of Homeland Security Screening Threshold Quantity (pounds): Release hazard 10,000 ($1.00% concentration). Clean Air Act: Accidental Release Prevention/Flammable Substances, (Section 112[r], Table 3), TQ 5 15,000 lb (6810 kg). Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 500 lb (227 kg). Reportable Quantity (RQ): 500 lb (227 kg). US DOT 49CFR172.101, Inhalation Hazardous Chemical. Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: Hazard Symbol: F, T; Risk phrases: R11; R23; R34; Safety phrases: S1/2; S16; S26; S36; S45 (see Appendix 4). WGK (German Aquatic Hazard Class): No value assigned. Description: Propyl chloroformate is a colorless liquid. Molecular weight 5 122.56; Boiling point 5 114116 C; Flash point 5 50 C. Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 4, Reactivity 2 . Insoluble in water; slowly decomposes. Potential Exposure: Propyl chloroformate is used in organic synthesis; as an intermediate for polymerization initiators; military poison gas. Incompatibilities: Oxidizers, water, and alcohol Permissible Exposure Limits in Air Protective Action Criteria (PAC)* TEEL-0: 0.75 ppm PAC-1: 2 ppm PAC-2: 3.7 ppm PAC-3: 11 ppm *AEGLs (Acute Emergency Guideline Levels) & ERPGs (Emergency Response Planning Guideline) are in bold face. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Absorbed through the skin. Harmful Effects and Symptoms Short Term Exposure: A lacrimator; vapors cause tearing. Corrosive to eyes, skin, and mucous membranes. May cause burns and permanent eye damage. Poisonous: may be fatal if inhaled, swallowed, or absorbed through skin. Long Term Exposure: May cause lung damage. Points of Attack: Lungs. Medical Surveillance: Lung function tests. Consider chest X-ray following acute overexposure. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If
2269
this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. If victim is conscious, administer water or milk. Do not induce vomiting. Keep victim quiet and maintain normal body temperature. Effects may be delayed; keep victim under observation. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—Red: Flammability Hazard: Store in a flammable liquid storage area or approved cabinet away from ignition sources and corrosive and reactive materials. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, well-ventilated area away from oxidizers. Where possible, automatically pump liquid from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of 5 gallons or more of this chemical should be grounded and bonded. Drums must be equipped with self-closing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: This compound requires a shipping label of “FLAMMABLE LIQUID, POISON, CORROSIVE,” It falls in Hazard Class 6.1 and Packing Group I. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Ventilate area of spill or leak. Absorb liquids in vermiculite, dry sand, earth,
2270
Propylene
peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Initial isolation and protective action distances Distances shown are likely to be affected during the first 30 min after materials are spilled and could increase with time. If more than one tank car, cargo tank, portable tank, or large cylinder involved in the incident is leaking, the protective action distance may need to be increased. You may need to seek emergency information from CHEMTREC at (800) 424-9300 or seek professional environmental engineering assistance from the US EPA Environmental Response Team at (908) 548-8730 (24-h response line). Small spills (From a small package or a small leak from a large package) First: Isolate in all directions (feet/meters) 100/30 Then: Protect persons downwind (miles/kilometers) Day 0.1/0.2 Night 0.2/0.3 Large spills (From a large package or from many small packages) First: Isolate in all directions (feet/meters) 200/60 Then: Protect persons downwind (miles/kilometers) Day 0.5/0.8 Night 0.8/1.3 Fire Extinguishing: This chemical is a flammable liquid. Poisonous gases, including hydrogen chloride and chlorine, are produced in fire. Small fires: Dry chemical, carbon dioxide extinguishers. Move container from fire area if you can do so without risk. Dike fire control water for later disposal; do not scatter the material. Keep unnecessary people away; isolate hazard area and deny entry. Stay upwind; keep out of low areas. Wear positive pressure breathing apparatus and special protective clothing. Isolate for 1/2 mile in all directions if tank car or truck is involved in fire. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any
signs of deforming), withdraw immediately to a secure position. Spray cooling water on containers that are exposed to flames until after fire is out. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. References US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Propyl Chloroformate. Washington, DC: Chemical Emergency Preparedness Program New Jersey Department of Health and Senior Services. (September 2001). Hazardous Substances Fact Sheet: Propyl Chloroformate. Trenton, NJ
Propylene
P:1230
Molecular Formula: C3H6 Common Formula: CH2QCHCH3 Synonyms: Isobutylene; Methylethene; Methylethylene; NCI-C50077; Propene; 1-Propene; Propileno (Spanish) CAS Registry Number: 115-07-1; (alt.) 676-63-1; (alt.) 33004-01-2 RTECS® Number: UC6470000 UN/NA & ERG Number: UN1077/115 EC Number: 204-062-1 [Annex I Index No.: 601-011-00-9] Regulatory Authority and Advisory Bodies Department of Homeland Security Screening Threshold Quantity (pounds): Release hazard 10,000 ($1.00% concentration). Carcinogenicity: IARC: Animal Inadequate Evidence; Human Inadequate Evidence, not classifiable as carcinogenic to humans, Group 3, 1994; NCI: Carcinogenesis Studies (inhalation); no evidence: mouse, rat. Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Clean Air Act: Accidental Release Prevention/Flammable Substances, (Section 112[r], Table 3), TQ 5 10,000 lb (4540 kg). EPCRA Section 313 Form R de minimis concentration reporting level: 1.0%. European/International Regulations: Hazard Symbol: F1; Risk phrases: R12; Safety phrases: S2; S9; S16; S33 (see Appendix 4). WGK (German Aquatic Hazard Class): Nonwater polluting agent. Description: Propylene is a colorless gas with a slight odor. The odor threshold is 23 ppm. Molecular weight 5 42.09; Specific gravity (H2O:1) 5 0.51 at 25 C; Boiling point 5 47 C; Freezing/Melting point 5 185 C; Flash point 5 Flammable gas (72 C); Autoignition temperature 5 455 C. Explosive limits: LEL 5 2.0%; UEL 5 11.1%. Hazard Identification (based on NFPA-704
Propylene M Rating System): Health 1, Flammability 4, Reactivity 1. Insoluble in water. Potential Exposure: Compound Description: Tumorigen. Propylene is used in the production of fabricated polymers, fibers, polypropylene resins, solvents, isopropyl alcohol, propylene dimer and trimer as gasoline components and detergent raw materials, propylene oxide, cumene, synthetic glycerol, isoprene, and oxo-alcohols. Incompatibilities: Violent reaction with oxidizers and many other compounds. Able to form unstable peroxides; can polymerize, especially in heat, direct sunlight, oxidizers and other chemicals. Permissible Exposure Limits in Air ACGIH TLV®[1]: 500 ppm/860 mg/m3 TWA, not classifiable as a human carcinogen. Protective Action Criteria (PAC) TEEL-0: 500 ppm PAC-1: 1500 ppm PAC-2: 10,000 ppm PAC-3: 20,000 ppm Australia: asphyxiant, 1993; Belgium: asphyxiant, 1993; Hungary: asphyxiant, 1993; Russia: STEL 100 mg/m3, 1993; Switzerland: MAK-W 10,000 ppm (17,500 mg/m3), 1999; United Kingdom: asphyxiant, 2000; the Netherlands: MAC-TGG 900 mg/m3, 2003; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: not classifiable as a human carcinogen. Russia[43] set a MAC of 3.0 mg/m3 in ambient air in residential areas both on a momentary and a daily average basis. The oxygen content should be tested regularly to ensure that it is at least 19% by volume. Permissible Concentration in Water: Russia[43] set a MAC of 0.5 mg/L in water bodies used for domestic purposes. Determination in Water: Octanolwater coefficient: Log Kow 5 1.8. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Propylene can affect you when breathed in. Exposure to high levels can cause you to feel dizzy and lightheaded. Very high levels can cause you to pass out from lack of oxygen. Death can result. Contact with liquefied propylene can cause frostbite. Long Term Exposure: Exposure may cause an irregular heartbeat. It may also damage the liver. Points of Attack: Liver, heart, liver. Medical Surveillance: If symptoms develop or overexposure is suspected, the following may be useful: liver function tests. Holter monitor (a special 24-h EKG to look for irregular heartbeat). First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately
2271
with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. If frostbite has occurred, seek medical attention immediately; do NOT rub the affected areas or flush them with water. In order to prevent further tissue damage, do NOT attempt to remove frozen clothing from frostbitten areas. If frostbite has NOT occurred, immediately and thoroughly wash contaminated skin with soap and water. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield when working with liquid unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Exposure to propylene is dangerous because it can replace oxygen and lead to suffocation. Only NIOSH/MSHA- or European Standard EN 149-approved self-contained breathing apparatus with a full face-piece operated in positive-pressure mode should be used in oxygen-deficient environments. Storage: Color Code—Red Stripe: Flammability Hazard: Store separately from all other flammable materials. Prior to working with this chemical you should be trained on its proper handling and storage. Before entering confined space where this chemical may be present, check to make sure that an explosive concentration is not a danger. Propylene must be stored to avoid contact with oxidizers (such as perchlorates, peroxides, permanganates, chlorates, and nitrates) since violent reactions occur. Store in tightly closed containers in a cool, well-ventilated area away from heat or direct sunlight. Sources of ignition, such as smoking and open flames, are prohibited where propylene is handled, used, or stored. Use only nonsparking tools and equipment, especially when opening and closing containers of propylene. Wherever propylene is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Piping should be electrically bonded and grounded. Procedures for the handling, use, and storage of propylene cylinders should be in compliance with OSHA 1910.101 and 1910.169, as with the recommendations of the Compressed Gas Association. Shipping: This compound requires a shipping label of “FLAMMABLE GAS.” It falls in Hazard Class 2.1.
2272
Propylene chlorohydrins
Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Establish forced ventilation to keep levels below explosive limit. Put on protective clothing and equipment. Remove tank or cylinder to an open area. Allow to bleed off slowly into atmosphere. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a flammable gas or liquid. Poisonous gases, including carbon dioxide and carbon monoxide, are produced in fire. Stop flow of gas. Use carbon dioxide or dry chemical. Use water spray, fog, or foam extinguishers. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers and protect firefighters. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Controlled incineration. References New York State Department of Health. (April 1986). Chemical Fact Sheet: Propylene. Albany, NY: Bureau of Toxic Substance Assessment New Jersey Department of Health and Senior Services. (May 2004). Hazardous Substances Fact Sheet: Propylene. Trenton, NJ
Propylene chlorohydrins Molecular Formula: C3H7ClO Common Formula: CH3CHClCH2OH
P:1240
Synonyms: 2-Chloro-1-propanol; 2-Chloropropanol; β-Chloropropyl alcohol; 2-Chloropropyl alcohol; 1Propanol, 2-chloro-; 1-Chloro-2-propanol with 2-chloro-1propanol (127-00-4) CAS Registry Number: 78-89-7 (2-chloropropan-1-ol); 127-00-4 (1-chloropropan-2-ol) RTECS® Number: UA8925000 UN/NA & ERG Number: UN2611/131 EC Number: 201-154-3 (2-chloropropan-1-ol); 204-819-6 (1-chloropropan-2-ol). Regulatory Authority and Advisory Bodies European/International Regulations: not listed in Annex 1. WGK (German Aquatic Hazard Class): No value assigned. Description: Propylene chlorohydrin is a colorless liquid. Molecular weight 5 94.55; Boiling point 5 133134 C; Flash point 5 52 C. Hazard Identification (based on NFPA704 M Rating System): Health 2, Flammability 2, Reactivity 0. Soluble in water. Potential Exposure: This material is used in organic synthesis. Incompatibilities: Strong oxidizers. Permissible Exposure Limits in Air 78-89-7 & 204-819-6 ACGIH TLV®[1]: 1 ppm/4 mg/m3 [skin], not classifiable as a human carcinogen. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Absorbed through the skin. Harmful Effects and Symptoms Short Term Exposure: Propylene chlorohydrin can affect you when breathed in and by passing through your skin. Contact can severely irritate and may burn the eyes. Breathing propylene chlorohydrin can irritate the nose and throat. Contact can irritate the skin. Overexposure may cause you to be lightheaded, unsteady, and drowsy. Long Term Exposure: No chronic health effects are known at this time. Points of Attack: Skin, eyes. Medical Surveillance: There is no special test for this chemical. However, if illness occurs or overexposure is suspected, medical attention is recommended. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide
Propylene glycol recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Where there is potential for exposure to propylene chlorohydrin, use a NIOSH/MSHA- or European Standard EN149-approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuous-flow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, wellventilated area away from strong oxidizers (such as chlorine, bromine, and fluorine). Sources of ignition, such as smoking and open flames, are prohibited where propylene chlorohydrin is used, handled, or stored in a manner that could create a potential fire or explosion hazard. Where possible, automatically transfer material from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of this chemical should be grounded and bonded. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: This compound requires a shipping label of “POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 6.1 and Packing Group II. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Ventilate area of spill or leak. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible liquid. Poisonous gases, including hydrogen chloride and carbon
2273
monoxide, are produced in fire. Use dry chemical, carbon dioxide, or foam extinguishers. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Dissolve or mix the material with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber. All federal, state, and local environmental regulations must be observed. Reference New Jersey Department of Health and Senior Services. (March 1998). Hazardous Substances Fact Sheet: Propylene Chlorohydrin. Trenton, NJ
Propylene glycol
P:1250
Molecular Formula: C3H8O2 Common Formula: CH3CHOHCH2OH Synonyms: 1,2-Dihydroxypropane; Methyl ethylene glycol; Methyl glycol; 1,2-Propanediol CAS Registry Number: 57-55-6 RTECS® Number: TY2000000 UN/NA & ERG Number: None assigned; UN1913 (combustible liquid; Note: must be preheated)/128 EC Number: 200-338-0 Regulatory Authority and Advisory Bodies US EPA Gene-Tox Program, Negative: SHE—clonal assay. US EPA, FIFRA, 1998 Status of Pesticides: Supported. Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. FDA—over-the-counter drug. Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: not listed in Annex 1. WGK (German Aquatic Hazard Class): 1—Low hazard to waters. Description: Propylene glycol is a colorless, odorless, syrupy liquid. Molecular weight 5 76.11; Boiling point 5 188 C; Specific gravity (H2O:1) 5 1.04 at 25 C;
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Propylene glycol
Freezing/Melting point 5 59 C; Flash point 5 99 C (cc); Autoignition temperature 5 371 C. Explosive limits: LEL 5 2.6%; UEL 5 12.5%. Hazard Identification (based on NFPA-704 M Rating System): Health 0, Flammability 1 (must be preheated), Reactivity 0; NJDHSS: Health 1, Flammability 2, Reactivity 0. Soluble in water. Potential Exposure: Compound Description: Agricultural Chemical; Mutagen; Reproductive Effector; Human Data; Hormone, Primary Irritant. Propylene glycol is used as a solvent, emulsifying agent, food and feed additive, flavoring agent; in the manufacturing of plastics; as a plasticizer, surface-active agent, antifreeze, solvent, disinfectant, hydroscopic agent; coolant in refrigeration systems; pharmaceutical; brake fluid; and many others. Incompatibilities: Contact with oxidizing agents, such as permanganates or dichromates, can cause a violent reaction. Permissible Exposure Limits in Air AIHA WEEL: 10 mg/m3 TWA. Protective Action Criteria (PAC) TEEL-0: 10 mg/m3 PAC-1: 10 mg/m3 PAC-2: 10 mg/m3 PAC-3: 500 mg/m3 United Kingdom: TWA 150 ppm, total vapor and particulates; STEL 10 mg/m3, particulates, 2000. Determination in Air: NIOSH Analytical Method #5523, Glycols. Determination in Water: Octanolwater coefficient: Log Kow 5 2 0.9. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Absorbed through the skin. Harmful Effects and Symptoms Short Term Exposure: Irritates the eyes, skin, and respiratory tract. Two fluid ounces (60 mL) has caused stupor which lasted for a few hours which was followed by complete recovery. Long Term Exposure: A mild allergen. Repeated or prolonged contact may cause skin sensitization and allergy. Therapeutic doses given for over a year have been associated with seizures; no further seizures occurred upon withdrawal of medication. Points of Attack: Skin. Medical Surveillance: Examination by a qualified allergist. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit.
Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. Polyethylene, Nitrile 1 PVC, butyl rubber; polyvinyl chloride, Tychem® (from E.I. du Pont de Nemours & Company), Trellchem™, and Responder™ are among the recommended protective materials. Butyl rubber, Nitrile, Neoprene, and Neoprene 1 natural rubber are among the glove materials. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—Green: General storage may be used. Prior to working with this chemical you should be trained on its proper handling and storage. Before entering confined space where this chemical may be present, check to make sure that an explosive concentration is not a danger. Store in a well-ventilated area away from ignition sources. Store in tightly closed containers in a cool, well-ventilated area away from oxidizers. Where possible, automatically pump liquid from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of 5 gallons or more of this chemical should be grounded and bonded. Drums must be equipped with self-closing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosionproof electrical equipment and fittings. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Establish forced ventilation to keep levels below explosive limit. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations.
Propylene glycol dinitrate It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible liquid. Poisonous gases are produced in fire. Use dry chemical, carbon dioxide, or alcohol foam extinguishers. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Dissolve or mix the material with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber. All federal, state, and local environmental regulations must be observed. References New York State Department of Health. (April 1986). Chemical Fact Sheet: Propylene Glycol. Albany, NY: Bureau of Toxic Substance Assessment New Jersey Department of Health and Senior Services. (September 2009). Hazardous Substances Fact Sheet: Propylene Glycol. Trenton, NJ
Propylene glycol dinitrate
P:1260
Molecular Formula: C3H6N2O6 Common Formula: CH3CHONO2CH2ONO2 Synonyms: PGDN; Propylene glycol-1,2-dinitrate; 1,2Propanediol, dinitrate; 1,2-Propylene glycol dinitrate Note: Otto fuel is primarily propylene glycol dinitrate. CAS Registry Number: 6423-43-4; 106602-80-6 (otto fuel) RTECS® Number: TY6300000 UN/NA & ERG Number: FORBIDDEN to be transported EC Number: 229-180-0
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Regulatory Authority and Advisory Bodies Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: not listed in Annex 1. WGK (German Aquatic Hazard Class): No value assigned. Description: Propylene glycol dinitrate is an explosive, colorless, high-boiling liquid (solid below 2 8 C) with a disagreeable odor. Molecular weight 5 166.11; Specific gravity (H2O:1) 5 1.23 at 25 C; Boiling point 5 (decomposes) 207 C at 760 mmHg; Freezing/Melting point 5 27.8 C; Vapor pressure 5 0.07 mmHg at 22 C. Flash point 5 99 C. Strong oxidizer. Slightly soluble in water; solubility 5 0.1%. Potential Exposure: Compound Description: Human Data; Primary Irritant. Propylene glycol dinitrate has been used as a torpedo propellant. The explosion potential is similar to ethylene glycol dinitrate. Incompatibilities: A strong oxidizer. Contact with ammonia compounds, amines, strong acids, reducing agents, combustible materials may result in fire and explosion. It is similar to ethylene glycol dinitrate in explosion potential. Propylene glycol dinitrate may explode if strongly shocked or heated. Permissible Exposure Limits in Air Conversion factor: 6.79 mg/m3 at 25 C & 1 atm. OSHA PEL: None. NIOSH REL: 0.05 ppm/0.3 mg/m3 TWA [skin]. ACGIH TLV®[1]: 0.05 ppm/0.34 mg/m3 TWA [skin]; BEIM issued for Methemoglobin inducers. Protective Action Criteria (PAC)* 6423-43-4 (propylene glycol dinitrate) & 106602-80-6 (otto fuel which is primarily propylene glycol dinitrate) TEEL-0: 0.05 ppm PAC-1: 0.17 ppm PAC-2: 1.0 ppm PAC-3: 13 ppm *AEGLs (Acute Emergency Guideline Levels) & ERPGs (Emergency Response Planning Guideline) are in bold face. DFG MAK: 0.05 ppm/0.34 mg/m3 TWA; Peak Limitation Category I(1) [skin]. Australia: TWA 0.05 ppm (0.3 mg/m3), [skin], 1993; Austria: MAK 0.05 ppm (0.3 mg/m3), [skin], 1999; Belgium: TWA 0.5 ppm (0.35 mg/m3), [skin], 1993; Denmark: TWA 0.02 ppm (0.2 mg/m3), [skin], 1999; Finland: TWA 0.02 ppm (0.2 mg/m3); STEL 0.06 ppm, [skin], 1999; France: VME 0.05 ppm (0.3 mg/m3), [skin], 1999; the Netherlands: MAC-TGG 0.3 mg/m3, [skin], 2003; Sweden: NGV 0.1 ppm (0.7 mg/m3), KTV 0.3 ppm (2 mg/ m3), [skin], 1999; Switzerland: MAK-W 0.05 ppm (0.35 mg/m3), [skin], 1999; United Kingdom: TWA 0.2 ppm (1.4 mg/m3); STEL 0.2 ppm, [skin], 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: TWA 0.05 ppm [skin]. Several states have set guidelines or
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Propylene glycol dinitrate
standards for propylene glycol dinitrate in ambient air[60] ranging from 3 μg/m3 (North Dakota) to 5 μg/m3 (Virginia) to 6 μg/m3 (Connecticut) to 7 μg/m3 (Nevada). Determination in Air: See OSHA Analytical Method 43. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Absorbed through the skin. Harmful Effects and Symptoms Short Term Exposure: Propylene glycol dinitrate can affect you when breathed in and by passing through your skin. Exposure can cause headaches, stuffy nose, eye irritation, a “drunken” feeling with impaired balance, visual disturbance. Higher exposures can interfere with the ability of the blood to carry oxygen (methemoglobinemia). This causes cyanosis, a bluish color to the skin and can lead to death. Propylene glycol dinitrate can cause the blood pressure to drop rapidly. Human volunteers at 0.2 ppm exposure exhibited headaches and disruption in visually evoked response. At 0.5 ppm, marked impairment in balance was noted. At 1.5 ppm eye irritation occurred, in addition.[53] Long Term Exposure: May cause liver and kidney damage. Points of Attack: Eyes, central nervous system, blood, liver, kidneys. Medical Surveillance: If symptoms develop or overexposure is suspected, the following may be useful: blood tests for methemoglobin level. Liver and kidney function tests. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. Note to physician: Treat for methemoglobinemia. Spectrophotometry may be required for precise determination of levels of methemoglobin in urine. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash
immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Where there is potential for exposures over 0.05 ppm, use a NIOSH/MSHA- or European Standard EN149-approved supplied-air respirator with a full facepiece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuous-flow mode; or use a NIOSH/MSHA- or European Standard EN149approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positivepressure mode. Storage: Explosive. Prior to working with this chemical you should be trained on its proper handling and storage. Propylene glycol dinitrate must be stored to avoid contact with ammonia compounds, amines, oxidizers, reducers, or combustible material since violent reactions occur. Store in tightly closed containers in a cool, well-ventilated area away from heat and avoid shocking or jolting containers. Where possible, automatically pump liquid from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of 5 gallons or more of this chemical should be grounded and bonded. Drums must be equipped with self-closing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: Dinitropropylene glycol is FORBIDDEN. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Ventilate area of spill or leak. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible liquid. Poisonous gases, including nitrogen oxides, are produced in fire. Use dry chemical, carbon dioxide, or alcohol foam extinguishers. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or
Propylene glycol monomethyl ether contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Dissolve or mix the material with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber. All federal, state, and local environmental regulations must be observed. Reference New Jersey Department of Health and Senior Services. (August 2005). Hazardous Substances Fact Sheet: Propylene Glycol Dinitrate. Trenton, NJ
Propylene glycol monomethyl ether P:1270 Molecular Formula: C4H10O2 Common Formula: CH3OCH2CHOHCH3 Synonyms: Dowtherm® 209; 1-Methoxy-2-hydroxypropane; 1-Methoxy-2-propanol; 2-Methoxy-1-methylethanol; PGME; Propylene glycol methyl ether CAS Registry Number: 107-98-2 RTECS® Number: UB7700000 UN/NA & ERG Number: UN3092/129 EC Number: 203-539-1 Regulatory Authority and Advisory Bodies Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Glycol ethers: Clean Air Act: Hazardous Air Pollutants (Title I, Part A, Section 112) includes mono- and di-ethers of ethylene glycol, diethyl glycol, and triethylene glycol Ra (OCH2CH2)naOR0 , where n 5 1, 2, or 3; R 5 alkyl or aryl groups; R0 5 R, H, or groups which when removed, yield glycol ethers with the structure: Ra(OCH2CH)naOH. Polymers are excluded from the glycol category. EPCRA Section 313: Certain glycol ethers are covered. Ra (OCH2CH2)naOR0 ; Where n 5 1, 2, or 3; R 5 alkyl C7 or less; or R 5 phenyl or alkyl substituted phenyl; R0 1 H, or alkyl C7 or less; or OR0 consisting of carboxylic ester, sulfate, phosphate, nitrate, or sulfonate. Form R de minimis concentration reporting level: 1.0%. Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%.
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European/International Regulations: Hazard Symbol: None assigned; Risk phrases: 10; Safety phrases: S2; S24 (see Appendix 4). WGK (German Aquatic Hazard Class): 1—Low hazard to waters. Description: Propylene glycol monomethyl ether is a colorless liquid with an ethereal odor. The odor threshold is 10 ppm. Molecular weight 5 90.14; Specific gravity (H2O:1) 5 0.96 at 25 C; Boiling point 5 120 C; Freezing/ Melting point 5 (sets to glass) 2 96 C; Vapor pressure 5 12 mmHg at 25 C; Flash point 5 36.1 C; Autoignition temperature 5 272 C. Explosive limits: LEL 5 1.6%; UEL 5 13.8%. Hazard Identification (based on NFPA-704 M Rating System): Health 0, Flammability 3, Reactivity 0. Soluble in water. Potential Exposure: Compound Description: Reproductive Effector; Human Data; Primary Irritant. Propylene glycol monomethyl ether is used as a solvent for coatings; cellulose esters and acrylics; acrylics dyes; inks; and stains. It may also be used as a heat-transfer fluid. Incompatibilities: Reacts with oxidizers, strong acids, acid chlorides, acid anhydrides, isocyanates, aluminum, and copper. Hygroscopic (i.e., absorbs moisture from the air). May slowly form reactive peroxides during prolonged storage. Permissible Exposure Limits in Air Conversion factor: 1 ppm 5 3.69 mg/m3 at 25 C & 1 atm. OSHA PEL: None. NIOSH REL: 100 ppm/360 mg/m3 TWA: 150 ppm/540 mg/ m3 STEL. ACGIH TLV®[1]: 100 ppm TWA; 150 ppm STEL. Protective Action Criteria (PAC) TEEL-0: 100 ppm PAC-1: 150 ppm PAC-2: 150 ppm PAC-3: 1250 ppm DFG MAK: 100 ppm/370 mg/m3 TWA; Peak Limitation Category I(2); Pregnancy Risk Group C. Austria: MAK 100 ppm (375 mg/m3), 1999; Belgium: TWA 100 ppm (369 mg/m3); STEL 150 ppm (553 mg/m3), 1993; Denmark: TWA 50 ppm (185 mg/m3), 1999; Finland: TWA 100 ppm (360 mg/m3); STEL 150 ppm, [skin], 1999; France: VME 100 ppm (360 mg/m3), 1999; Norway: TWA 50 ppm (180 mg/m3), 1999; the Netherlands: MAC-TGG 375 mg/m3, 2003; Switzerland: MAK-W 100 ppm (360 mg/ m3), KZG-W 200 ppm (720 mg/m3), 1999; United Kingdom: TWA 100 ppm (375 mg/m3); STEL 300 ppm, [skin], 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: STEL 150 ppm. Several states have set guidelines or standards for PGME in ambient air[60] ranging from 3.65.4 mg/m3 (North Dakota) to 6.0 mg/m3 (Virginia) to 7.2 mg/m3 (Connecticut). Determination in Air: Use NIOSH Analytical Method #2554; OSHA Analytical Method 99. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Absorbed through the skin.
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Propylene glycol monomethyl ether
Harmful Effects and Symptoms Short Term Exposure: Propylene glycol monomethyl ether can affect you when breathed in and by passing through your skin. Contact can irritate the eyes and skin. Exposure can irritate the nose and throat. Very high levels may cause lung, liver, and kidney damage. Very high levels of propylene glycol monomethyl ether may cause central nervous system depression, dizziness and lightheadedness, and unconsciousness. Long Term Exposure: Causes skin dryness, dermatitis. May cause liver and kidney damage. Can irritate the lungs; bronchitis may develop. Points of Attack: Eyes, skin, respiratory system, central nervous system. Medical Surveillance: If symptoms develop or overexposure is suspected, the following may be useful: liver and kidney function tests; lung function tests. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Where there is potential for exposures over 100 ppm, use a NIOSH/MSHA- or European Standard EN 149-approved respirator with an organic vapor cartridge/canister. More protection is provided by a full-facepiece respirator than by a half-mask respirator, and even greater protection is provided by a powered air-purifying respirator. Where there is potential for high exposures, use a NIOSH/MSHA- or European Standard EN 149-approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuous-flow mode; or use a NIOSH/ MSHA- or European Standard EN 149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode.
Storage: Color Code—Red: Flammability Hazard: Store in a flammable liquid storage area or approved cabinet away from ignition sources and corrosive and reactive materials. Prior to working with this chemical you should be trained on its proper handling and storage. Before entering confined space where this chemical may be present, check to make sure that an explosive concentration is not a danger. Store in tightly closed containers in a cool, well-ventilated area away from strong oxidizers (such as chlorine, bromine, and fluorine). Where possible, automatically transfer material from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of this chemical should be grounded and bonded. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: 1-Methoxy-2-propanol requires a shipping label of “FLAMMABLE LIQUID.” It falls in Hazard Class 3. Packing Group III. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Establish forced ventilation to keep levels below explosive limit. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a flammable liquid. Poisonous gases, including nitrogen oxides, are produced in fire. Use dry chemical, carbon dioxide, or foam extinguishers. Water may be ineffective. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for
Propyleneimine firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Dissolve or mix the material with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber. All federal, state, and local environmental regulations must be observed. Reference New Jersey Department of Health and Senior Services. (August 2005). Hazardous Substances Fact Sheet: Propylene Glycol Monomethyl Ether. Trenton, NJ
Propyleneimine
P:1280
Molecular Formula: C3H7N Synonyms: Aziridina, 2-metil (Spanish); Aziridine, 2methyl-; 2-Methylazacyclopropane; 2-Methylaziridine; 2Methylethylenimine; 2-Methylethylen imine; Propilenimina (Spanish); Propylene imine; 1,2-Propyleneimine CAS Registry Number: 75-55-8 RTECS® Number: CM8050000 UN/NA & ERG Number: UN1921 (stabilized)/131 EC Number: 200-878-7 [Annex I Index No.: 613-033-00-6] Regulatory Authority and Advisory Bodies Department of Homeland Security Screening Threshold Quantity (pounds): Release hazard 10,000 ($1.00% concentration). Carcinogenicity: IARC: Human No Adequate Data, Animal Sufficient Evidence, possibly carcinogenic to humans, Group 2B, 1999; NTP: 11th Report on Carcinogens, 2004: Reasonably anticipated to be a human carcinogen; NIOSH: Potential occupational carcinogen. US EPA Gene-Tox Program, Positive: Carcinogenicity— mouse/rat; SHE—clonal assay; Positive: Cell transform.— RLV F344 rat embryo; Host-mediated assay; Positive: E. coli polA without S9; Histidine reversion—Ames test; Positive: In vitro UDS—human fibroblast; S. cerevisiae— homozygosis; Positive: S. pombe—reversion; Positive/dose response: Cell transform.—BALB/c-3T3. Banned or Severely Restricted (Belgium, Sweden) (UN).[13] Toxic Substance (World Bank).[15] Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Clean Air Act: Hazardous Air Pollutants (Title I, Part A, Section 112); Accidental Release Prevention/Flammable Substances, (Section 112[r], Table 3), TQ 5 10,000 lb (4540 kg). US EPA Hazardous Waste Number (RCRA No.): P067. RCRA, 40CFR261, Appendix 8 Hazardous Constituents. Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 10,000 lb (4540 kg). Reportable Quantity (RQ): 1 lb (0.454 kg). EPCRA Section 313 Form R de minimis concentration reporting level: 0.1%.
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California Proposition 65 Chemical: Cancer 1/1/88. Canada, WHMIS, Ingredients Disclosure List Concentration 0.1%. European/International Regulations: Hazard Symbol: F, T 1 , N; Risk phrases: R45; R11; R26/27/28; R41; R51/53; Safety phrases: S53; S45; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): 3—Severe hazard to waters. Description: Propyleneimine is a fuming, colorless, oily liquid with a strong ammonia-like odor. Molecular weight 5 57.11; Specific gravity (H2O:1) 5 0.81 at 25 C; Boiling point 5 66.7 C; Freezing/Melting point 5 63 C; Flash Vapor pressure 5 112 mmHg at 25 C; point 5 2 10 C (cc). Explosive limits: LEL 5 2.3%; UEL 5 15.1%. Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 4, Reactivity 0. Soluble in water. Potential Exposure: Compound Description: Tumorigen, Mutagen. Propyleneimine is used in the modification of latex surface coating resins; in the production of polymers for use in the paper and textile industries as coatings and adhesives. Incompatibilities: Reacts with acids, strong oxidizers, water, carbonyl compounds, quinones, sulfonyl halides. May explode in heat. Subject to violent polymerization in contact with acids. Hydrolyzes in water to form methylethanolamine. Permissible Exposure Limits in Air OSHA PEL: 2 ppm/5 mg/m3 TWA [skin]. NIOSH REL: 2 ppm/5 mg/m3 TWA [skin]; A potential occupational carcinogen; Limit exposure to lowest feasible concentration. See NIOSH Pocket Guide, Appendix A. ACGIH TLV®[1]: 2 ppm/5 mg/m3 TWA; 0.4 ppm/1 mg/m3 STEL [skin]; confirmed animal carcinogen with unknown relevance to humans. NIOSH IDLH: (potential occupational carcinogen) 100 ppm. Protective Action Criteria (PAC)* TEEL-0: 0.2 ppm PAC-1: 0.4 ppm PAC-2: 12 ppm PAC-3: 23 ppm *AEGLs (Acute Emergency Guideline Levels) & ERPGs (Emergency Response Planning Guideline) are in bold face. DFG MAK: [skin] Carcinogen Category 2; Germ Cell Mutation Category 3B. Australia: TWA 2 ppm (5 mg/m3), [skin], carcinogen, 1993; Austria: [skin], carcinogen, 1999; Denmark: TWA 2 ppm (5 mg/m3), [skin], 1999; Finland: STEL 2 ppm (5 mg/m3), [skin], carcinogen, 1999; France: carcinogen, 1993; Japan: 2 ppm (4.7 mg/m3), [skin], 1999; the Netherlands: MACTGG 0.6 μg/m3, 2003; the Philippines: TWA 2 ppm (5 mg/ m3), [skin], 1993; Russia: TWA 2 ppm, 1993; Switzerland: MAK-W 2 ppm (5 mg/m3), [skin], carcinogen, 1999; Turkey: TWA 2 ppm (5 mg/m3), [skin], 1993; United
2280
Propyleneimine
Kingdom: carcinogen, 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: confirmed animal carcinogen with unknown relevance to humans. Several states have set guidelines or standards for propyleneimine in ambient air[60] ranging from zero (North Dakota) to 12 μg/m3 (Pennsylvania) to 50 μg/m3 (Connecticut and Virginia) to 119 μg/m3 (Nevada). Determination in Air: No method available. Routes of Entry: Inhalation, skin absorption, ingestion, eye and/or skin contact. Harmful Effects and Symptoms Short Term Exposure: Severely irritates the eyes, skin, and respiratory tract. Contact may cause skin burns and permanent eye damage. Symptoms of exposure include inflammation and blistering of the skin, eye, and upper respiratory tract; irritation, nausea, itching, and periodic vomiting. Headache, dizziness, and pain in the temple. Shortness of breath; and increased nasal and laryngeal secretion are seen. It is toxic after acute exposure. LD50 5 (oral-rat) 19 mg/kg (highly toxic). Long Term Exposure: Caused skin drying and dermatitis. A potential occupational carcinogen. May affect the kidneys. Points of Attack: Eyes, skin. Cancer site in animals: nasal cavity, breast, brain, blood or bone marrow. Medical Surveillance: NIOSH lists the following tests: complete blood count; granulocytic leukemia. Before beginning employment and at regular times after that, for those with frequent or potentially high exposures, the following are recommended: lung function tests. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash.
Respirator Selection: NIOSH: At concentrations above the NIOSH REL, or where there is no REL, at any detectable concentration: SCBAF: Pd,Pp (APF 5 10,000) (any self-contained breathing apparatus that has a full facepiece and is operated in a pressure-demand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary self-contained breathing apparatus operated in a pressuredemand or other positive-pressure mode). Escape: GmFS (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or back-mounted canister providing protection against the compound of concern] or SCBAE (any appropriate escape-type, self-contained breathing apparatus). Storage: Color Code—Red: Flammability Hazard: Store in a flammable liquid storage area or approved cabinet away from ignition sources and corrosive and reactive materials. Prior to working with this chemical you should be trained on its proper handling and storage. Propyleneimine must be stored to avoid contact with acids and strong oxidizers (such as chlorine, bromine, and fluorine) because violent reactions occur. Store in tightly closed containers in a cool, well-ventilated area. Sources of ignition, such as smoking and open flames, are prohibited where propyleneimine is used, handled, or stored in a manner that could create a potential fire or explosion hazard. Metal containers involving the transfer of 5 gallons or more of Propyleneimine should be grounded and bonded. Drums must be equipped with self-closing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of propyleneimine. A regulated, marked area should be established where this chemical is handled, used, or stored in compliance with OSHA Standard 1910.1045. Shipping: This compound requires a shipping label of “FLAMMABLE LIQUID.” It falls in Hazard Class 3 and Packing Group I. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Avoid breathing vapors; avoid bodily contact with the material. Toxic gases, including oxides of nitrogen and carbon monoxide, are released in a fire. Do not handle broken packages without protective equipment. Wash away any material which may have contacted the body with copious amounts of water or soap with water. Use water spray to disperse vapors and dilute standing pools of liquid. Keep sparks and flames away. Attempt to stop leak if it can be done without hazard. Ventilate area of spill or leak. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive
Propylene oxide concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a flammable liquid. Poisonous gases are produced in fire. Use dry chemical, carbon dioxide, or alcohol foam extinguishers. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant ($100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. Controlled incineration (incinerator equipped with a scrubber or thermal unit to reduce nitrogen oxides emissions). References Dermer, O. C., & Ham, G. E. (1969). Ethyleneimine and Other Aziridines. New York: Academic Press US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Propyleneimine. Washington, DC: Chemical Emergency Preparedness Program New Jersey Department of Health and Senior Services. (August 2005). Hazardous Substances Fact Sheet: Propylene Imine. Trenton, NJ
Propylene oxide
P:1290
Molecular Formula: C3H6O Synonyms: AD 6; Epoxypropane; 1,2-Epoxypropane; 2,3Epoxypropane; Methyl ethylene oxide; Methyl oxirane; NCI-C50099; Oxido de propileno (Spanish); Oxyde de propylene (French); Oxirane, methyl-; Propane, 1,2-epoxy-; Propene oxide; Propylene epoxide; 1,2-Propylene oxide
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CAS Registry Number: 75-56-9 RTECS® Number: TZ2975000 UN/NA & ERG Number: UN1280/127 EC Number: 200-879-2 [Annex I Index No.: 603-055-00-4] Regulatory Authority and Advisory Bodies Department of Homeland Security Screening Threshold Quantity (pounds): Release hazard 10,000 ($1.00% concentration). Carcinogenicity: IARC: Human Inadequate Evidence, Animal Sufficient Evidence, possibly carcinogenic to humans, Group 2B, 1997; NTP: 11th Report on Carcinogens, 2004: Reasonably anticipated to be a human carcinogen; EPA: Sufficient evidence from animal studies; inadequate evidence or no useful data from epidemiologic studies; NIOSH: Potential occupational carcinogen; NCI: Carcinogenesis Studies (inhalation); clear evidence: mouse; some evidence: rat; equivocal evidence: rat US EPA Gene-Tox Program, Positive: Carcinogenicity— mouse/rat; Cell transform.—SA7/SHE EPA; Positive: N. crassa—reversion; D. melanogaster sex-linked lethal EPA; Positive: S. pombe—reversion EPA; Negative: Rodent dominant lethal EPA; Positive: CHO gene mutation. Highly Reactive Substance and Explosive (World Bank).[15] Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Clean Air Act: Hazardous Air Pollutants (Title I, Part A, Section 112); Accidental Release Prevention/Flammable Substances, (Section 112[r], Table 3), TQ 5 10,000 lb (4540 kg). Clean Water Act: Section 311 Hazardous Substances/RQ 40CFR117.3 (same as CERCLA, see below); Section 313 Water Priority Chemicals (57FR41331, 9/9/92). Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 10,000 lb (4540 kg). Reportable Quantity (RQ): 100 lb (45.4 kg). EPCRA Section 313 Form R de minimis concentration reporting level: 0.1%. California Proposition 65 Chemical: Cancer 1/1/88. Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: Hazard Symbol: F 1 , T; R45; R46; R12; R20/21/22; R36/37/38; Safety phrases: S53; S45 (see Appendix 4). WGK (German Aquatic Hazard Class): 3—Severe hazard to waters. Description: Propylene oxide is a colorless liquid with an ether-like odor. Molecular weight 5 58.09; Boiling point 5 34.4 C; Specific gravity (H2O:1) 5 0.83 at 25 C; Freezing/Melting point 5 112.2 C; Vapor pressure 5 445 mmHg at 25 C; Flash point 5 37.2 C; Autoignition temperature 5 450 C. Explosive limits: LEL 5 2.3%; UEL 5 3638.5%. Hazard Identification (based on NFPA704 M Rating System): Health 3, Flammability 4, Reactivity 2. Soluble in water; solubility 5 41%. Potential Exposure: Compound Description: Agricultural Chemical; Tumorigen, Mutagen; Reproductive Effector;
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Propylene oxide
Human Data; Hormone, Primary Irritant. Propylene oxide is used as an intermediate in the production of polyether polyols and propylene glycol; as a fumigant; in the production of adducts as urethane foam ingredients; in detergent manufacture; as a component in brake fluids. Incompatibilities: Reacts with strong oxidizers, anhydrous metal chlorides, chlorine, iron, strong acids, caustics and peroxides. Polymerization may occur due to high temperatures or contamination with alkalis, aqueous acids, amines, metal chlorides, and acidic alcohols. Attacks some plastics, coatings, and rubber. Permissible Exposure Limits in Air Conversion factor: 1 ppm 5 2.38 mg/m3 at 25 C & 1 atm. OSHA PEL: 100 ppm/240 mg/m3 TWA. NIOSH REL: A potential occupational carcinogen. [skin]; Limit exposure to lowest feasible concentration. See NIOSH Pocket Guide, Appendix A. ACGIH TLV®[1]: 2 ppm/4.8 mg/m3 TWA, sensitizer; confirmed animal carcinogen with unknown relevance to humans. (2000) NIOSH IDLH: 400 ppm (potential occupational carcinogen). Protective Action Criteria (PAC)* TEEL-0: 2 ppm PAC-1: 73 ppm PAC-2: 290 ppm PAC-3: 870 ppm *AEGLs (Acute Emergency Guideline Levels) & ERPGs (Emergency Response Planning Guideline) are in bold face. DFG MAK: [skin] Carcinogen Category 2. Australia: TWA 20 ppm (50 mg/m3), carcinogen, 1993; Austria: carcinogen, 1999; Belgium: TWA 20 ppm (48 mg/ m3), 1993; Denmark: TWA 5 ppm (12 mg/m3), [skin], 1999; Finland: TWA 5 ppm (12 mg/m3), carcinogen, 1999; France: VME 20 ppm (50 mg/m3), carcinogen, 1999; the Netherlands: MAC-TGG 6 mg/m3, 2003; the Philippines: TWA 100 ppm (240 mg/m3), 1993; Russia: STEL 1 mg/m3, [skin], 1993; Sweden: NGV 5 ppm (12 mg/m3), KTV 10 ppm (25 mg/m3), 1999; Switzerland: MAK-W 2.5 ppm (6 mg/m3), carcinogen, 1999; Turkey: TWA 100 ppm (240 mg/m3), 1993; United Kingdom: TWA 5 ppm (12 mg/ m3), carcinogen, 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: confirmed animal carcinogen with unknown relevance to humans. Russia set a MAC of 0.08 mg/m3 for ambient air in residential areas. Several states have set guidelines or standards for propylene oxide in ambient air[60] ranging from 0.0833 μg/m3 (Kansas) to 1.0 μg/m3 (Connecticut) to 15.0 μg/m3 (Massachusetts) to 167.0 μg/m3 (New York) to 250.0 μg/m3 (South Carolina) to 500.0 μg/ m3 (North Dakota) to 625.0 μg/m3 (Pennsylvania) to 850.0 μg/m3 (Virginia) to 1190.0 μg/m3 (Nevada). Determination in Air: Use NIOSH Analytical Method #1612. Propylene oxide; OSHA Analytical Method 88. Permissible Concentration in Water: Russia has set[35] a MAC value of 0.01 mg/L in water bodies used for domestic
purposes and 0.005 mg/L in water bodies used for fishery purposes. Determination in Water: Octanolwater coefficient: Log Kow 5 ,0.02. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Propylene oxide may irritate or burn the skin, eyes, and respiratory tract. Contact with the liquid can cause blindness and death. This material is moderately toxic by inhalation and ingestion. It may cause irreversible and reversible changes. Skin contact with the material or solutions of the material cause irritation; diluted solutions are more irritating than undiluted materials. Dermatitis (red, inflamed skin) is common. Exposure may cause mild depression of the central nervous system, and eye, nasal, and lung irritation. Other signs and symptoms of acute exposure may include headache, nausea, vomiting, and unconsciousness. Victims may appear as if they are in a drunken stupor. Pulmonary edema may occur. Long Term Exposure: Repeated or prolonged contact may cause skin sensitization. This substance is possibly carcinogenic to humans. May decrease fertility in males and females. May cause lung damage; pneumonia may develop. Points of Attack: Eyes, skin, respiratory system. Cancer site in animals: nasal cavity, stomach. Medical Surveillance: Before beginning employment and at regular times after that, the following are recommended: lung function tests. If symptoms develop or overexposure is suspected, the following may be useful: liver function tests. Examination of the eyes and vision. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Speed in removing material from skin is of extreme importance. Shampoo hair promptly if contaminated. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. Teflon™ and butyl rubber are
Propylene oxide among the recommended protective materials. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: NIOSH: At concentrations above the NIOSH REL, or where there is no REL, at any detectable concentration: SCBAF: Pd,Pp (APF 5 10,000) (any self-contained breathing apparatus that has a full facepiece and is operated in a pressure-demand or other positivepressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: GmFS (APF 5 50) [any air-purifying, fullface-piece respirator (gas mask) with a chin-style, front- or back-mounted canister providing protection against the compound of concern] or SCBAE (any appropriate escape-type, self-contained breathing apparatus). Storage: Color Code—Red: Flammability Hazard: Store in a flammable liquid storage area or approved cabinet away from ignition sources and corrosive and reactive materials. Prior to working with this chemical you should be trained on its proper handling and storage. Before entering confined space where this chemical may be present, check to make sure that an explosive concentration is not a danger. Propylene oxide must be stored to avoid contact with anhydrous metal chlorides, iron, strong acids (such as hydrochloric, sulfuric, and nitric), strong bases and peroxides, copper or copper alloys since violent reactions occur. Propylene oxide will attack some forms of plastics, rubber, and coatings. Store in tightly closed containers in a cool, well-ventilated area. Sources of ignition, such as smoking and open flames, are prohibited where propylene oxide is used, handled, or stored in a manner that could create a potential fire or explosion hazard. Metal containers involving the transfer of 5 gallons or more of propylene oxide should be grounded and bonded. Drums must be equipped with self-closing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of propylene oxide. Wherever propylene oxide is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. A regulated, marked area should be established where this chemical is handled, used, or stored in compliance with OSHA Standard 1910.1045. Shipping: This compound requires a shipping label of “FLAMMABLE LIQUID.” It falls in Hazard Class 3 and Packing Group I. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup
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is complete. Remove all ignition sources. Establish forced ventilation to keep levels below explosive limit. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a flammable liquid. Poisonous gases are produced in fire. Extinguish with dry chemical, carbon dioxide, water spray, fog, or foam. Firefighting should be done from a safe distance or from a protected location. Wear self-contained (positive pressure if available) breathing apparatus and full protective clothing. Isolate for 1/2 mile in all directions if tank car or truck is involved in fire. Move container from area if you can do so without risk. Spray cooling water on containers that are exposed to flames until well after fire is out. For massive fire in cargo area, use unmanned hose holder or monitor nozzles; if this is impossible, withdraw from area and let fire burn. Withdraw immediately in case of rising sound from venting safety device or any discoloration of tank due to fire. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Concentrated waste containing no peroxides—discharge liquid at a controlled rate near a pilot flame. Concentrated waste containing peroxides— perforation of a container of the waste from a safe distance followed by open burning.[22] References Bogyo, D. A., Lande, S. S., Meylan, W. M., Howard, P. H., & Santodonato, J. (March 1980). Syracuse Research Corp. Center for Chemical Hazard Assessment, Investigation of
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Propyl isocyanate
Selected Potential Environmental Contaminants: Epoxides, Report EPA-560/11-08-005. Washington, DC: US Environmental Protection Agency US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Propylene Oxide. Washington, DC: Chemical Emergency Preparedness Program New York State Department of Health. (April 1986). Chemical Fact Sheet: Propylene Oxide. Version 2. Albany, NY: Bureau of Toxic Substance Assessment New Jersey Department of Health and Senior Services. (April 2002). Hazardous Substances Fact Sheet: Propylene Oxide. Trenton, NJ
Propyl isocyanate
P:1300
Molecular Formula: C4H7NO Common Formula: C3H7NCO Synonyms: 1-Isocyanatopropane; Isocyanic acid, propyl ester; m-Propyl isocyanate; 1-Propyl isocyanate CAS Registry Number: 110-78-1 RTECS® Number: NR190000 UN/NA & ERG Number: UN2482/155 EC Number: 203-803-6 Regulatory Authority and Advisory Bodies Canada, WHMIS, Ingredients Disclosure List Concentration 0.1%. European/International Regulations: not listed in Annex 1. WGK (German Aquatic Hazard Class): 1—Low hazard to waters. Description: Propyl isocyanate is a colorless to light yellow liquid with a sharp odor. Molecular weight 5 85.12; Flash point 5 23 C. Insoluble; reacts with water. Potential Exposure: This material is used in making other chemicals and insecticides. Incompatibilities: Violent reactions with strong oxidizers, water, amines, strong bases, and alcohols. Permissible Exposure Limits in Air Protective Action Criteria (PAC) Isocyanate-bearing waste (as CNs, n.o.s.). TEEL-0: 5 mg/m3 PAC-1: 15 mg/m3 PAC-2: 25 mg/m3 PAC-3: 25 mg/m3 Routes of Entry: Inhalation, ingestion, skin and/or eye contact. May be absorbed by the skin. Harmful Effects and Symptoms Short Term Exposure: Propyl isocyanate can affect you when breathed in and possibly by passing through your skin. Irritates the eyes, skin, nose, throat, and lungs. Prolonged contact may cause severe irritation and permanent eye damage. Very high exposures can cause pulmonary edema, a medical emergency that can be delayed for several hours. This can cause death.
Long Term Exposure: Very irritating substances may affect the lungs. Many isocyanates cause an asthma-like lung allergy. It is not known for certain if propyl isocyanate does. Points of Attack: Lungs. Medical Surveillance: For those with frequent or potentially high exposure the following are recommended before beginning work and at regular times after that: lung function tests. These may be normal if the person is not having an attack at the time of the test. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Medical observation is recommended for 2448 h after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Where there is potential for exposures to propyl isocyanate, use a NIOSH/MSHA- or European Standard EN149-approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuous-flow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Propyl isocyanate must be stored to avoid contact with strong oxidizers, water, amines, strong bases (such as sodium hydroxide or potassium hydroxide) and alcohols since violent reactions occur. Store in tightly closed
n-Propyl nitrate containers in a cool, well-ventilated area away from heat, light, and moisture. Sources of ignition, such as smoking and open flames, are prohibited where propyl isocyanate is handled, used, or stored. Metal containers involving the transfer of 5 gallons or more of propyl isocyanate should be grounded and bonded. Drums must be equipped with selfclosing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of propyl isocyanate. Shipping: This compound requires a shipping label of “POISONOUS/TOXIC MATERIALS, FLAMMABLE LIQUID.” It falls in Hazard Class 6.1 and Packing Group I. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Ventilate area of spill or leak. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Initial isolation and protective action distances Distances shown are likely to be affected during the first 30 min after materials are spilled and could increase with time. If more than one tank car, cargo tank, portable tank, or large cylinder involved in the incident is leaking, the protective action distance may need to be increased. You may need to seek emergency information from CHEMTREC at (800) 424-9300 or seek professional environmental engineering assistance from the US EPA Environmental Response Team at (908) 548-8730 (24-h response line). Small spills (From a small package or a small leak from a large package) First: Isolate in all directions (feet/meters) 300/100 Then: Protect persons downwind (miles/kilometers) Day 0.8/1.2 Night 1.7/2.7 Large spills (From a large package or from many small packages) First: Isolate in all directions (feet/meters) 2500/800 Then: Protect persons downwind (miles/kilometers) Day 6.0/9.6 Night 7.01/11.01 distance can be larger in certain atmospheric conditions Fire Extinguishing: Propyl isocyanate is a flammable liquid. Poisonous gases are produced in fire, including hydrogen cyanide and oxides of nitrogen. Use dry chemical, CO2, or foam extinguishers. Do not use water. Vapors are heavier than air and will collect in low areas. Vapors may travel
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long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Reference New Jersey Department of Health and Senior Services. (April 2001). Hazardous Substances Fact Sheet: Propyl Isocyanate. Trenton, NJ
n-Propyl nitrate
P:1310
Molecular Formula: C3H7NO2 Common Formula: CH3CH2CH2NO2 Synonyms: Nitrate de propyle normal (French); Nitric acid, propyl ester; Propyl nitrate; Nitric acid, n-propyl ester; Propyl ester of nitric acid CAS Registry Number: 627-13-4 RTECS® Number: UK0350000 UN/NA & ERG Number: UN1865/131 EC Number: 210-985-0 Regulatory Authority and Advisory Bodies Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: not listed in Annex 1. WGK (German Aquatic Hazard Class): No value assigned. Description: n-Propyl nitrate is a colorless to pale yellow liquid with an ether-like odor. Molecular weight 5 105.11; Specific gravity (H2O:1) 5 1.07 at 25 C; Boiling point 5 110.6 C; Freezing/Melting point 5 100 C; Vapor pressure 5 18 mmHg at 25 C; Flash point 5 20 C. Explosive limits: LEL 5 2%; UEL 5 100%. Hazard Identification (based on NFPA-704 M Rating System): Health 2, Flammability 3, Reactivity 3 (Oxidizer). Slightly soluble in water. Potential Exposure: Propyl nitrate has been used as an intermediate as a rocket propellant and as an ignition improver in diesel fuels. Incompatibilities: Reacts with strong oxidizers, combustible materials. A shock-sensitive explosive. May explode on
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n-Propyl nitrate
heating. Forms explosive mixtures with combustible materials. Permissible Exposure Limits in Air Conversion factor: 1 ppm 5 4.30 mg/m3 at 25 C & 1 atm. OSHA PEL: 25 ppm/110 mg/m3 TWA. NIOSH REL: 25 ppm/105 mg/m3 TWA; 40 ppm/170 mg/ m3 STEL. ACGIH TLV®[1]: 25 ppm/107 mg/m3 TWA; 40 ppm/ 172 mg/m3 STEL; BEIM issued for methemoglobin inducers. NIOSH IDLH: 500 ppm. Protective Action Criteria (PAC) TEEL-0: 25 ppm PAC-1: 40 ppm PAC-2: 100 ppm PAC-3: 500 ppm DFG MAK: 25 ppm/110 mg/m3 TWA; Peak Limitation Category II(2). Australia: TWA 25 ppm (110 mg/m3); STEL 40 ppm, 1993; Austria: MAK 25 ppm (110 mg/m3), 1999; Belgium: TWA 25 ppm (107 mg/m3); STEL 40 ppm (172 mg/m3), 1993; Denmark: TWA 25 ppm (110 mg/m3), 1999; Finland: TWA 25 ppm (105 mg/m3), 1999; Norway: TWA 20 ppm (90 mg/ m3), 1999; the Philippines: TWA 25 ppm (110 mg/m3), 1993; the Netherlands: MAC-TGG 110 mg/m3, 2003; Switzerland: MAK-W 25 ppm (110 mg/m3), 1999; Turkey: TWA 25 ppm (110 mg/m3), 1993; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: STEL 40 ppm. Several states have set guidelines or standards for propyl nitrate in ambient air[60] ranging from 1.051.70 mg/m3 (North Dakota) to 1.75 mg/m3 (Virginia) to 2.1 mg/m3 (Connecticut) to 2.5 mg/m3 (Nevada). Determination in Air: Use NIOSH II(3), Method #S-227; OSHA Analytical Method 7. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: None listed for humans according to NIOSH[2] but other sources[24] state that vapor inhalation causes low blood pressure, hypotony, hemoglobin defect, anoxia, and cyanosis. In animals: irritation of the eyes, skin; methemoglobinemia, anoxia, cyanosis, dyspnea (breathing difficulty), weakness, dizziness, headache. Points of Attack: May attack the blood. Medical Surveillance: NIOSH lists the following tests: whole blood (chemical/metabolite), methemoglobin; Complete blood count; urinalysis. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions,
including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Note to physician: Consider treatment for methemoglobinemia. Spectrophotometry may be required for precise determination of levels of methemoglobin in urine. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Up to 250 ppm: Sa (APF 5 10) (any supplied-air respirator). Up to 500 ppm: Sa:Cf (APF 5 25) (any supplied-air respirator operated in a continuous-flow mode) or SCBAF (APF 5 50) (any self-contained breathing apparatus with a full face-piece) or SaF (APF 5 50) (any supplied-air respirator with a full face-piece). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd,Pp (APF 5 10,000) (any self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: GmFS* [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or backmounted canister providing protection against the compound of concern] or SCBAE (any appropriate escape-type, self-contained breathing apparatus). *End-of-service life indicator (ESLI) required. Storage: (1) Color Code—Red: Flammability Hazard: Store in a flammable liquid storage area or approved cabinet away from ignition sources and corrosive and reactive materials. (2) Color Code—Yellow: Reactive Hazard; Store in a location separate from other materials, especially flammables and combustibles. Prior to working with this chemical you should be trained on its proper handling and storage. Before entering confined space where this chemical may be present, check to make sure that an explosive concentration is not a danger. Protect containers against physical damage. Outdoor or detached storage is preferred. Indoor storage should be in a flammable liquid storage room. Propyl nitrate should be isolated from combustible materials and oxidizing agents. Wear Neoprene™ gloves,
Prothoate plastic coverall, and self-contained breathing apparatus. Where possible, automatically pump liquid from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of 5 gallons or more of this chemical should be grounded and bonded. Drums must be equipped with self-closing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. See OSHA Standard 1910.104 and NFPA 43A Code for the Storage of Liquid and Solid Oxidizers for detailed handling and storage regulations. Shipping: This compound requires a shipping label of “FLAMMABLE LIQUID.” It falls in Hazard Class 3 and Packing Group II. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Establish forced ventilation to keep levels below explosive limit. After covering the spills with soda ash, mix and spray with water. Scoop into a bucket of water and let it stand for 2 h. Neutralize with 6M-HCl and pass into the drain with sufficient water. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a flammable liquid. Poisonous gases are produced in fire. Use dry chemical, carbon dioxide, or alcohol foam extinguishers. On fires in which containers are not exposed, use dry chemical, foam, or carbon dioxide. Water spray may be ineffective as an extinguishing agent. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. Use water from unmanned monitors or householders to keep fire-exposed containers cool. If cooling streams are ineffective (venting sound increases in
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volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Incineration: large quantities of material may require nitrogen oxide removal by catalytic or scrubbing processes.[22] An alternative route suggested involves pouring over soda ash, neutralizing with HCl, and flushing to the drain with water. Reference New Jersey Department of Health and Senior Services. (July 2001). Hazardous Substances Fact Sheet: n-Propyl Nitrate. Trenton, NJ
Prothoate
P:1320
Molecular Formula: C9H20NO3PS2 Synonyms: AC18682; American Cyanamid 18682; O,ODiethyldithiophosphorylacetic acid N-monoisopropylamide; O,O-Diethyl S-(N-isopropylcarbamoylmethyl) dithiophosphate; O,O-Diethyl S-(N-isopropylcarbamoylmethyl) phosphorodithioate; O,O-Diethyl S-isopropylcarbamoylmethyl phosphorodithioate; ENT 24,652; FAC; FAC20; Fostion; Isopropyl diethyldithiophosphorylacetamide; N-Isopropyl-2mercaptoacetamide S-ester with O,O-diethyl phosphorodithioate; L 343; N-Monoisopropylamide of O,O-diethyldithiophosphorylacetic acid; Oleofac; Phosphorodithioic acid O,O-diethyl esters, ester with n-isopropyl-2-mercaptoacetamide; Phosphorodithioic acid, O,O-diethyl S-(2-[(1methylethyl)amino]-2-oxoethyl) ester; Telefos; Trimethoate CAS Registry Number: 2275-18-5 RTECS® Number: TD8225000 UN/NA & ERG Number: UN2783 (organophosphorus pesticides, solid, toxic)/152 EC Number: 218-893-2 [Annex I Index No.: 015-032-00-0] Regulatory Authority and Advisory Bodies Banned or Severely Restricted (Malaysia) (UN).[13] Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 100/10,000 lb (45.4/4540 kg). Reportable Quantity (RQ): 100 lb (45.4 kg). US DOT Regulated Marine Pollutant (49CFR172.101, Appendix B). US DOT 49CFR172.101, Inhalation Hazard Chemical as organophosphates. European/International Regulations: Hazard Symbol: T1 , N; Risk phrases: R27/28; R52/53; Safety phrases: S1/2; S28; S36/37; S45; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): No value assigned. Description: Prothoate is an amber to yellow crystalline solid with a camphor-like odor. Molecular weight 5 285.39; Boiling point 5 135 C at 0.1 mm; Freezing/Melting point 5 29 C. Hazard Identification (based on NFPA-704 M
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Prothoate
Rating System): Health 4, Flammability 1, Reactivity 0. Slightly soluble in water. Potential Exposure: Those involved in the manufacture, formulation, and application of the systemic acaricide and insecticide. Permissible Exposure Limits in Air Protective Action Criteria (PAC) TEEL-0: 0.35 mg/m3 PAC-1: 1 mg/m3 PAC-2: 1.7 mg/m3 PAC-3: 7.5 mg/m3 Determination in Air: OSHA versatile sampler-2; Toluene/ Acetone; Gas chromatography/Flame photometric detection for sulfur, nitrogen, or phosphorus; NIOSH Analytical Method (IV) Method #5600, Organophosphorus pesticides. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: This is a highly toxic material capable of causing death or permanent injury due to exposures during normal use. Small doses at frequent intervals are additive. Similar to parathion. Symptoms may include nausea, vomiting, abdominal cramps, diarrhea, excessive salivation, headache, giddiness, dizziness, weakness, muscle twitching, difficult breathing, blurring or dimness of vision, and loss of muscle coordination. Death may occur from failure of the respiratory center, paralysis of the respiratory muscles, intense bronchoconstriction, or all the three. Long Term Exposure: Cholinesterase inhibitor; cumulative effect is possible. This chemical may damage the nervous system with repeated exposure, resulting in convulsions, respiratory failure. May cause liver damage. Points of Attack: Respiratory system, lungs, central nervous system, cardiovascular system, skin, eyes, plasma and red blood cell cholinesterase. Medical Surveillance: Before employment and at regular times after that, the following are recommended: plasma and red blood cell cholinesterase levels (tests for the enzyme poisoned by this chemical). If exposure stops, plasma levels return to normal in 12 weeks while red blood cell levels may be reduced for 13 months. When cholinesterase enzyme levels are reduced by 25% or more below preemployment levels, risk of poisoning is increased, even if results are in lower ranges of “normal.” Reassignment to work not involving organophosphate or carbamate pesticides is recommended until enzyme levels recover. If symptoms develop or overexposure occurs, repeat the above tests as soon as possible and get an examination of the nervous system. Also, consider complete blood count. Consider chest X-ray following acute overexposure. Do not drink any alcoholic beverages before or during use. Alcohol promotes absorption of organic phosphates. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the
skin, remove contaminated clothing and wash immediately with soap and water. Speed in removing material from skin is of extreme importance. Shampoo hair promptly if contaminated. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Keep victim quiet and maintain normal body temperature. Effects may be delayed; keep victim under observation. If material has been ingested, induce vomiting with ipecac. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, wellventilated area. Where possible, automatically transfer material from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of this chemical should be grounded and bonded. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: This compound requires a shipping label of “POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 6.1 and Packing Group I. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Ventilate area of spill or leak. Stay upwind; keep out of low areas. Ventilate closed spaces before entering them. Do not touch spilled
Pyrene material; stop leak if you can do it without risk. Use water spray to reduce vapors. Small spills: take up with sand or other noncombustible absorbent material and place into containers for later disposal. Small dry spills: with clean shovel place material into clean, dry container and cover; move containers from spill area. Large spills: dike far ahead of spill for later disposal. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: Poisonous gases, including nitrogen oxides, sulfur oxides, phosphorus oxides, are produced in fire. This material may burn but does not readily ignite. For small fires, use dry chemical, carbon dioxide, water spray, or foam. For large fires, use water spray, fog, or foam. In fighting fires, stay upwind; keep out of low areas. Move containers from fire area if you can do it without risk. Fight fire from maximum distance. Dike fire control water for later disposal; do not scatter the material. Wear positive pressure breathing apparatus and special protective clothing. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: In accordance with 40CFR165, follow recommendations for the disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by contacting your local or federal environmental control agency or by contacting your regional EPA office. Reference US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Prothoate. Washington, DC: Chemical Emergency Preparedness Program
Pyrene
2289
P:1330
Molecular Formula: C16H10 Synonyms: Benzo(def)phenanthrene; Pireno (Spanish); Pyren (German); β-Pyrene CAS Registry Number: 129-00-0 UN/NA & ERG Number: UN1325 (flammable solid)/133 RTECS® Number: UR2450000 EC Number: 204-927-3 Regulatory Authority and Advisory Bodies Carcinogenicity: IARC: Animal Inadequate Evidence; Human No Adequate Data, not classifiable as carcinogenic to humans, Group 3, 1987; EPA: Not Classifiable as to human carcinogenicity. US EPA Gene-Tox Program, Negative: Cell transform.— BALB/c-3T3; SHE—clonal assay; Negative: Cell transform.—mouse embryo; Negative: Cell transform.—RLV F344 rat embryo; Negative: In vitro cytogenetics—nonhuman; Host-mediated assay; Negative: Histidine reversion— Ames test; In vivo SCE—nonhuman; Negative: Sperm morphology—mouse; In vitro UDS—human fibroblast; Negative: V79 cell culture—gene mutation; Inconclusive: Carcinogenicity—mouse/rat; Mammalian micronucleus; Inconclusive: In vitro SCE—nonhuman. Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. OSHA, 29CFR1910 Specifically Regulated Chemicals (See CFR 1910.1002) as coal tar pitch volatiles. RCRA 40CFR268.48; 61FR15654, Universal Treatment Standards: Wastewater (mg/L), 0.067; Nonwastewater (mg/kg), 8.2. RCRA 40CFR264, Appendix 9; TSD Facilities Ground Water Monitoring List. Suggested test method(s) (PQL μg/L): 8100 (200); 8270 (10). Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 1000/10,000 lb (454/4540 kg). Reportable Quantity (RQ): 5000 lb (2270 kg). Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: not listed in Annex 1. WGK (German Aquatic Hazard Class): No value assigned. Description: Pyrene is a colorless crystalline solid when pure or pale yellow plates (impure). Polynuclear aromatic hydrocarbons (PAHs) are compounds containing multiple benzene rings and are also called polycyclic aromatic hydrocarbons. Solids and solutions have a blue fluorescence (Merck Index). Molecular weight 5 202.26; Boiling point 404 C at 760 mmHg[2]; Freezing/Melting point 5 151.2 C.[2] Flash point 5 199 C. Explosive limits: LEL 5 0.6%; UEL 5 3.9%. Hazard Identification (based on NFPA-704 M Rating System): Health 1, Flammability 2, Reactivity 0. Practically insoluble in water. Potential Exposure: Compound Description (Toxicity evaluation)[77]: Tumorigen, Mutagen. Primary Irritant. Pyrene is used as an industrial chemical and in biochemical research.
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Pyrene
Permissible Exposure Limits in Air NIOSH IDLH: 80 mg/m3. Protective Action Criteria (PAC) TEEL-0: 0.75 mg/m3 PAC-1: 2.5 mg/m3 PAC-2: 1.7 mg/m3 PAC-3: 15 mg/m3 DFG MAK: [skin]. Russia set a MAC of 0.3 mg/m3 in work-place air. Determination in Air: Use NIOSH Analytical Method #5506 polynuclear aromatic hydrocarbons by HPLC; NIOSH Analytical Method #5515, Polynuclear aromatic hydrocarbons by GC; OSHA Analytical Method ID-58. Permissible Concentration in Water: Zero is recommended for maximum protection of human health.[6] Kansas[61] has set a guideline for pyrene in drinking water of 0.029 μg/L. The World Health Organization (WHO) recommends a maximum of 2 μg/L for specific PAHs, but this list does not include pyrene. Determination in Water: Octanolwater coefficient: Log Kow 5 4.885.32. Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Can be absorbed through the skin. Harmful Effects and Symptoms Short Term Exposure: Pyrene is a skin irritant, a suspected mutagen; and an equivocal tumor-causing agent. Workers exposed to 35 mg/m3 of pyrene exhibited some teratogenic effects. Pyrene is a polycyclic aromatic hydrocarbon (PAH). The acute toxicity of pure PAHs appears low when administered orally or dermally to rats or mice. Human exposure to PACs or PAHs is almost exclusively via the gastrointestinal and respiratory tracts, and approximately 99% is ingested in the diet. Despite the high concentrations of pyrene to which humans may be exposed through food, there is currently little information available to implicate diet-derived PAHs as the cause of serious health effects. Long Term Exposure: The DFG[3] states that PAHs are present at particularly high levels in coal tar oils and related pyrolysis products of organic materials and are carcinogenic (category 1) in animal studies. Points of Attack: Skin, respiratory system, bladder, liver, kidneys. Medical Surveillance: Preplacement and regular physical examinations are indicated for workers having contact with acenaphthene in the workplace. NIOSH lists: complete blood count; chest X-ray; pulmonary function tests: Forced Vital Capacity; Forced Expiratory Volume (1 s); photopatch testing; sputum cytology; urinalysis (routine); cytology, hematuria.[2] First Aid: Skin Contact[52]: Flood all areas of body that have contacted the substance with water. Do not wait to remove contaminated clothing; do it under the water stream. Use soap to help assure removal. Isolate contaminated clothing when removed to prevent contact by others. Eye Contact: Remove any contact lenses at once. Immediately flush eyes well with copious quantities of water or normal
saline for at least 2030 min. Seek medical attention. Inhalation: Leave contaminated area immediately; breathe fresh air. Proper respiratory protection must be supplied to any rescuers. If coughing, difficult breathing, or any other symptoms develop, seek medical attention at once, even if symptoms develop many hours after exposure. Ingestion: Contact a physician, hospital, or poison center at once. If the victim is unconscious or convulsing, do not induce vomiting or give anything by mouth. Assure that this airway is open and lay him on his side with his head lower than his body and transport immediately to a medical facility. If conscious and not convulsing, give a glass of water to dilute the substance. Vomiting should not be induced without a physician’s advice. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: NIOSH: At any detectable concentration over 0.1 mg/m3: SCBAF: Pd,Pp (APF 5 10,000) (any NIOSH/MSHA- or European Standard EN 149-approved self-contained breathing apparatus that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary, self-contained breathing apparatus operated in a pressuredemand or other positive-pressure mode). Escape: GmFOv100 (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or backmounted organic vapor canister having an N100, R100, or P100 filter] or SCBAE (any appropriate escape-type, selfcontained breathing apparatus). Storage: Color Code—Red: Flammability Hazard: Store in a flammable materials storage area. Prior to working with this chemical you should be trained on its proper handling and storage. Store in a cool, dry place. Shipping: Flammable solids, organic, n.o.s. require a shipping label of “FLAMMABLE MATERIALS.” It falls in Hazard Class 4.1 and Packing Group II. Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Remove all sources of ignition and dampen spilled material with toluene to avoid airborne dust, then transfer material to a suitable container. Ventilate the spill area and use absorbent dampened with toluene to pick up remaining material. Wash surfaces well
Pyrethrins or pyrethrum with soap and water. Seal all wastes in vapor-tight plastic bags for eventual disposal. Collect powdered material in the most convenient and safe manner and deposit in sealed containers. Ventilate area after cleanup is complete. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a combustible solid. Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Poisonous gases are produced in fire. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: Dissolve or mix the material with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber. All federal, state, and local environmental regulations must be observed.[22] References US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Pyrene. Washington, DC: Chemical Emergency Preparedness Program US EPA. (April 1975). Identification of Organic Compounds in Effluents from Industrial Sources, EPA-560/ 3-75-002 Eller, P. M., Cassinelli, M. E. (Eds.). (1998). NIOSH Manual of Analytical Methods (NMAM®) (4th ed.). 2nd Supplement. National Institute for Occupational Safety and Health, DHHS (NIOSH), Publication No. 98-119. Cincinnati, OH
Pyrethrins or pyrethrum
P:1340
Molecular Formula: C2021H2830O35; C20H28O3/ C21H28O5/C21H30O3/C22H30O5/C21H28O3/C22H28O5 Synonyms: Buhach; Chrysanthemum cinerareaefolium; Cinerin I; Cinerin II; Dalmation insect flowers; Firmotox; Insect powder; Jasmolin I; Jasmolin II; Piretrina (Spanish);
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Pyrethrin I; Pyrethrin II; Pyrethrum; Pyrethrum insecticide; Trieste flowers CAS Registry Number: 8003-34-7; 121-21-1 (I); 121-29-9 (II) RTECS® Number: UR4200000 UN/NA & ERG Number: UN2902 (Pesticides, liquid, toxic, n.o.s.)/151 EC Number: 232-319-8; 204-455-8 [Annex I Index No.: 613-023-00-1] (I); 204-462-6 [Annex I Index No.: 613-02400-7] (II) Regulatory Authority and Advisory Bodies US EPA, FIFRA 1998 Status of Pesticides: Canceled. Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. Type I: Clean Water Act: Section 311 Hazardous Substances/RQ 40CFR117.3 (same as CERCLA, see below). US EPA Hazardous Waste Number (RCRA No.): P008. RCRA, 40CFR261, Appendix 8 Hazardous Constituents. Reportable Quantity (RQ): 1 lb (0.454 kg). Type II: Clean Water Act: Section 311 Hazardous Substances/RQ 40CFR117.3 (same as CERCLA, see below). Reportable Quantity (RQ): 1 lb (0.454 kg). European/International Regulations (I &II): Hazard Symbol: Xn, N; Risk phrases: R0/21/22; R50/53; Safety phrases: S2; S13; S60; S61 (see Appendix 4). WGK (German Aquatic Hazard Class): 3—Severe hazard to waters. Description: The pyrethrins are a variable mixture of compounds which are found in pyrethrum flowers: cinerin, jasmolin, and pyrethrin. Pyrethrins are a brown, viscous oil or solid. Molecular weight 5 316378; 372.45; Specific gravity (H2O:1) 5 1.0 (approx.) at 25 C; Boiling point 5 170 C at 0.1 mm (decomposition); Flash point 5 8288 C. Hazard Identification (based on NFPA-704 M Rating System): Health 2, Flammability 1, Reactivity 0. Insoluble in water. Potential Exposure: Compound Description: Agricultural Chemical; Reproductive Effector; Human Data; Natural Product. Pyrethrins are used as an ingredient of various contact insecticides. Those engaged in the isolation, formulation, or application of these materials. Incompatibilities: Violent reaction with strong oxidizers, alkaline materials. Permissible Exposure Limits in Air OSHA PEL: 5 mg/m3 TWA. NIOSH REL: 5 mg/m3 TWA. ACGIH TLV®[1]: 5 mg/m3 TWA; not classifiable as a human carcinogen. NIOSH IDLH: 5000 mg/m3. Protective Action Criteria (PAC) TEEL-0: 1 mg/m3 PAC-1: 3 mg/m3 PAC-2: 20 mg/m3 PAC-3: 100 mg/m3
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Pyrethrins or pyrethrum
DFG MAK: 5 mg/m3, inhalable fraction, danger of skin sensitization; Peak Limitation Category II(2). Arab Republic of Egypt: TWA 5 mg/m3, 1993; Australia: TWA 5 mg/m3, 1993; Austria: MAK 5 mg/m3, 1999; Belgium: TWA 5 mg/m3, 1993; Denmark: TWA 5 mg/m3, 1999; Finland: TWA 5 mg/m3; STEL 10 mg/m3, 1999; France: VME 5 mg/m3, 1999; the Netherlands: MAC-TGG 5 mg/m3, 2003; Norway: TWA 5 mg/m3, 1999; Thailand: TWA 5 mg/m3, 1993; Turkey: TWA 5 mg/m3, 1993; United Kingdom: TWA 5 mg/m3; STEL 10 mg/m3, 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: not classifiable as a human carcinogen. Several states have set guidelines or standards for pyrethrum in ambient air[60] ranging from 16.7 μg/m3 (New York) to 50.0 μg/m3 (Florida and South Carolina) to 50.0100.0 μg/m3 (North Dakota) to 80.0 μg/m3 (Virginia) to 100.0 μg/m3 (Connecticut) to 119.0 μg/m3 (Nevada). Determination in Air: Use NIOSH Analytical Method (IV) #5008, Pyrethrum; OSHA Analytical Method 7.[18] Determination in Water: Fish Tox: 2.38748000 ppb (HIGH). Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Pyrethrum can affect you when breathed in and by passing through your skin. Irritates the eyes and respiratory tract. High exposure can affect the nervous system causing headache, nausea, vomiting, fatigue, and restlessness and rhinorrhea (discharge of thin nasal mucus). Long Term Exposure: High or repeated exposure can cause lung allergy (with cough, wheezing, and/or shortness of breath) or hay fever symptoms (sneezing, runny or stuffy nose). Allergic “pneumonia” can also occur with cough, chest pain, breathing difficulty, and abnormal chest X-ray. Repeated attacks may lead to permanent scarring. Skin allergy may also develop with rash and itching, even with lower exposures. Skin contact can cause rash with redness, blisters, and intense itching. A severe generalized allergy can occur with weakness and collapse. Human Tox 5 68.09339 ppb. Chronic Human Carcinogen Level (CHCL) (LOW). Points of Attack: Respiratory system, skin, central nervous system. Medical Surveillance: Before beginning employment and at regular times after that, the following are recommended: lung function tests. These may be normal if the person is not having an attack at the time of the test. Consider chest X-ray if lung symptoms are present. Evaluation by a qualified allergist, including careful exposure history and special testing, may help diagnose skin allergy. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the
skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear eye protection to prevent any possibility of eye contact. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: 50 mg/m3: CcrOv95 (APF 5 10) [Any air-purifying half-mask respirator with organic vapor cartridge(s) in combination with an N95, R95, or P95 filter. The following filters may also be used: N99, R99, P99, N100, R100, P100] or Sa (APF 5 10) (any supplied-air respirator). 125 mg/m3: Sa:Cf (APF 5 25) (any supplied-air respirator operated in a continuous-flow mode) or PaprOvHie (APF 5 25) (any powered air-purifying respirator with an organic vapor cartridge in combination with a high-efficiency particulate filter). 250 mg/m3: CcrFOv100 (APF 5 50) [Any air-purifying full-face-piece respirator equipped with organic vapor cartridge(s) in combination with an N100, R100, or P100 filter] or PaprTOvHie (APF 5 50) [any powered, air-purifying respirator with a tight-fitting face-piece and organic vapor cartridge(s) in combination with a high-efficiency particulate filter] or SCBAF (APF 5 50) (any self-contained breathing apparatus with full face-piece) or SaF (APF 5 50) (any supplied-air respirator with a full face-piece). 5000 mg/m3: SaF: Pd,Pp (APF 5 2000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd, Pp (APF 5 10,000) (any self-contained breathing apparatus that has a full face-piece and is operated in a pressuredemand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: GmFOv100 (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or backmounted organic vapor canister having an N100, R100, or P100 filter] or SCBAE (any appropriate escape-type, selfcontained breathing apparatus).
Pyridine Note: Substance reported to cause eye irritation or damage; may require eye protection. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Pyrethrum must be stored to avoid contact with oxidizers (such as perchlorates, peroxides, permanganates, chlorates, and nitrates) and alkalines since violent reactions occur. Store in tightly closed containers in a cool, well-ventilated area. Where possible, automatically transfer material from drums or other storage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of this chemical should be grounded and bonded. Wherever this chemical is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: Pesticides, liquid, toxic, n.o.s. require a shipping label of “POISONOUS/TOXIC MATERIALS.” They fall in Hazard Class 6.1. and Packing Group I to III. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Ventilate area of spill or leak. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Soil Adsorption Index (Koc): 100,000 (estimate). Fire Extinguishing: This chemical is a combustible liquid. Poisonous gases, including acid fumes, are produced in fire. Use dry chemical, carbon dioxide, or alcohol foam extinguishers. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained
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breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Reference New Jersey Department of Health and Senior Services. (August 2002). Hazardous Substances Fact Sheet: Pyrethrum. Trenton, NJ
Pyridine
P:1345
Molecular Formula: C5H5N Synonyms: Azabenzene; Azine; CP 32; NCI-C55301; Pyridin (German) CAS Registry Number: 110-86-1 RTECS® Number: UR8400000 UN/NA & ERG Number: UN1282/129 EC Number: 203-809-9 [Annex I Index No.: 613-002-00-7] Regulatory Authority and Advisory Bodies Carcinogenicity: IARC: Animal Limited Evidence; Human Inadequate Evidence, not classifiable as carcinogenic to humans, Group 3, 2000; NCI: Carcinogenesis studies (water); clear evidence: mouse; equivocal evidence: rat; NTP: Carcinogenesis studies (drinking water); some evidence: rat. US EPA Gene-Tox Program, Positive/dose response: In vitro SCE—nonhuman. Air Pollutant Standard Set. See below, “Permissible Exposure Limits in Air” section. US EPA Hazardous Waste Number (RCRA No.): U196, DO38. RCRA, 40CFR261, Appendix 8 Hazardous Constituents. RCRA Toxicity Characteristic (Section 261.24), Maximum Concentration of Contaminants, regulatory level, 5.0 mg/L. RCRA 40CFR268.48; 61FR15654, Universal Treatment Standards: Wastewater (mg/L), 0.014; Nonwastewater (mg/ kg), 16. RCRA 40CFR264, Appendix 9; TSD Facilities Ground Water Monitoring List. Suggested test method(s) (PQL μg/ L): 8240 (5); 8270 (10). Reportable Quantity (RQ): 1000 lb (454 kg). EPCRA Section 313 Form R de minimis concentration reporting level: 1.0%. California Proposition 65 Chemical: Cancer 5/17/02. Canada, WHMIS, Ingredients Disclosure List Concentration 1.0%. European/International Regulations: Hazard Symbol: F, Xn; Risk phrases: R11; R20/21/22; Safety phrases: S2; S26; S28 (see Appendix 4). WGK (German Aquatic Hazard Class): 2—Hazard to waters. Description: Pyridine is a colorless liquid with a nauseating, fish-like odor. The odor threshold is 0.17 ppm. Molecular weight 5 79.11; Specific gravity (H2O:1) 5 0.98 at 25 C; Boiling point 5 115.6 C. Melting/Freezing point 5 242.2 C; Vapor pressure 5 16 mmHg at 25 C;
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Pyridine
Flash point 5 20 C; Autoignition temperature 5 482 C. Explosive limits: LEL 5 1.8%; UEL 5 12.4%. Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 3, Reactivity 0. Soluble in water. Potential Exposure: Compound Description: Tumorigen, Mutagen. Primary Irritant. Pyridine is used as a solvent in the chemical industry and as a denaturant for ethyl alcohol; as an intermediate in the production of pesticides; in pharmaceuticals; in the manufacture of paints, explosives, dyestuffs, rubber, vitamins, sulfa drugs, and disinfectants. Incompatibilities: Violent reaction with strong oxidizers, strong acids, chlorosulfonic acid, maleic anhydride, oleum iodine. Permissible Exposure Limits in Air Conversion factor: 1 ppm 5 3.24 mg/m3 at 25 C & 1 atm. OSHA PEL: 5 ppm/15 mg/m3 TWA. NIOSH REL: 5 ppm/15 mg/m3 TWA. ACGIH TLV®[1]: 1 ppm/3.1 mg/m3 TWA. NIOSH IDLH: 1000 ppm. Protective Action Criteria (PAC) TEEL-0: 1 ppm PAC-1: 3 ppm PAC-2: 5 ppm PAC-3: 1000 ppm DFG MAK: [skin] 5 ppm/16 mg/m3 TWA; Peak Limitation Category II(2). Arab Republic of Egypt: TWA 5 ppm (15 mg/m3), 1993; Australia: TWA 5 ppm (15 mg/m3), 1993; Austria: MAK 5 ppm (15 mg/m3), 1999; Belgium: TWA 5 ppm (16 mg/ m3), 1993; Denmark: TWA 5 ppm (15 mg/m3), 1999; Finland: TWA 5 ppm (15 mg/m3); STEL 10 ppm (30 mg/ m3), [skin], 1999; France: VME 5 ppm (15 mg/m3), VLE 10 ppm, 1999; the Netherlands: MAC-TGG 0.9 mg/m3, 2003; Norway: TWA 5 ppm (15 mg/m3), 1999; the Philippines: TWA 5 mg/m3, 1993; Poland: MAC (TWA) 5 mg/m3; MAC (STEL) 30 mg/m3, 1999; Russia: STEL 5 mg/m3, 1993; Sweden: NGV 5 ppm (16 mg/m3), KTV 10 ppm (35 mg/m3), 1999; Switzerland: MAK-W 5 ppm (15 mg/m3), KZG-W 10 ppm (30 mg/m3), 1999; Turkey: TWA 5 ppm (15 mg/m3), 1993; United Kingdom: TWA 5 ppm (16 mg/m3); STEL 10 ppm (33 mg/m3), 2000; Argentina, Bulgaria, Columbia, Jordan, South Korea, New Zealand, Singapore, Vietnam: ACGIH TLV®: TWA 5 ppm. The Czech Republic: MAC 5.0 mg/m3.[35] Russia[35, 43] has also set a MAC of 0.08 mg/m3 for the ambient air in residential areas both on a momentary and a daily average basis. Several states have set guidelines or standards for pyridine in ambient air[60] ranging from 2.0 μg/m3 (New York) to 150 μg/m3 (Indiana) to 150.0300.0 μg/m3 (North Dakota) to 250.0 μg/m3 (Virginia) to 300.0 μg/m3 (Connecticut, Florida) to 357.0 μg/m3 (Nevada). Determination in Air: Use NIOSH Analytical Method #1613[18]; OSHA Analytical Method 7. Permissible Concentration in Water: EPA[32] has suggested a permissible ambient goal of 207 μg/L. Russia[43] set a MAC of 200 μg/L in water bodies used for domestic
purposes and 10 μg/L in water bodies used for fishery purposes. Determination in Water: Octanolwater coefficient: Log Kow 5 0.65. Routes of Entry: Inhalation of vapor, percutaneous absorption of liquids, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: Irritates the eyes, skin, and respiratory tract. May affect the central nervous system; can cause stomach upset, headache, dizziness, lightheadedness, confusion, coma, and death. Inhalation: May cause nose and throat irritation at low levels. Above 5 ppm, the odor may no longer be detected but a characteristic taste may remain. Exposures of 612 ppm have caused headache, dizziness, nervousness, trouble sleeping, nausea, and vomiting. Skin: Contact with liquid may cause painful irritation and firstdegree burns. Longer contact may cause second-degree burns. Eyes: Vapors may cause irritation. Contact with liquid can cause irritation, burns, and permanent eye damage. Ingestion: 23 mL (1/151/10 fl oz) may cause loss of appetite, nausea, fatigue, and depression. Swallowing 1/2 cup has resulted in vomiting, diarrhea, fever, abdominal pain, bluish tint to the skin, confusion, hallucinations, severe lung congestion, and death. Long Term Exposure: Affects the central nervous system, brain, liver, and kidneys. Can cause skin allergy. Ingestion of about 2 mL (1/10 fl oz) three times/day for a prolonged period resulted in lever and kidney damage and death. Long-term inhalation of levels of 125 ppm in addition to the symptoms listed above may result in damage to the nervous system. Points of Attack: Eyes, skin, central nervous system, liver, kidneys, gastrointestinal tract. Medical Surveillance: NIOSH lists the following tests: Expired Air; liver function tests; urinalysis. If symptoms develop or overexposure is suspected, the following may be useful: examination of the nervous system; interview for brain effects, kidney function tests. Evaluation by a qualified allergist, including careful exposure history and special testing, may help diagnose skin allergy. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide
Pyridine recommendations on the most protective glove/clothing material for your operation. Polyethylene is among the recommended protective materials. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear splash-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: 125 ppm: Sa:Cf (APF 5 25) (any supplied-air respirator operated in a continuous-flow mode) or PaprOv (APF 5 25) [any powered, air-purifying respirator with organic vapor cartridge(s)]. 250 ppm: CcrFOv (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or back-mounted acid gas canister] or GmFOv (APF 5 50) [any air-purifying, fullface-piece respirator (gas mask) with a chin-style, front- or back-mounted organic vapor canister] or PaprTOv (APF 5 50) [any powered, air-purifying respirator with a tight-fitting face-piece and organic vapor cartridge(s)] or SCBAF (APF 5 50) (any self-contained breathing apparatus with a full face-piece) or SaF (APF 5 50) (any supplied-air respirator with a full face-piece). 1000 ppm: SaF: Pd,Pp (APF 5 2000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode). Emergency or planned entry into unknown concentrations or IDLH conditions: SCBAF: Pd, Pp (APF 5 10,000) (any self-contained breathing apparatus that has a full face-piece and is operated in a pressuredemand or other positive-pressure mode) or SaF: Pd,Pp: ASCBA (APF 5 10,000) (any supplied-air respirator that has a full face-piece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary self-contained breathing apparatus operated in a pressure-demand or other positive-pressure mode). Escape: GmFOv (APF 5 50) [any air-purifying, full-face-piece respirator (gas mask) with a chin-style, front- or back-mounted organic vapor canister] or SCBAE (any appropriate escapetype, self-contained breathing apparatus). Note: Substance causes eye irritation or damage; eye protection needed. Storage: Color Code—Red: Flammability Hazard: Store in a flammable liquid storage area or approved cabinet away from ignition sources and corrosive and reactive materials. Prior to working with this chemical you should be trained on its proper handling and storage. Before entering confined space where this chemical may be present, check to make sure that an explosive concentration is not a danger. Pyridine must be stored to avoid contact with strong oxidizers (such as chloride, bromine, and fluorine), strong acids (such as hydrochloride, sulfuric, and nitric), chlorosulfonic acid, maleic anhydride, and oleum iodine because violent reactions occur. Sources of ignition, such as smoking and open flames, are prohibited where pyridine is used, handles,
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or stored in a manner that could create a potential fire or explosion hazard. Metal containers used in the transfer of 5 gallons or more of pyridine should be grounded and bonded. Drums must be equipped with self-closing valves, pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening and closing containers of pyridine. Wherever pyridine is used, handled, manufactured, or stored, use explosion-proof electrical equipment and fittings. Shipping: This compound requires a shipping label of “FLAMMABLE LIQUID, POISONOUS/TOXIC MATERIALS.” It falls in Hazard Class 3 and Packing Group II. Spill Handling: Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Establish forced ventilation to keep levels below explosive limit. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the buildup of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: This chemical is a flammable liquid. Poisonous gases, including nitrogen oxides and cyanides, are produced in fire. Use dry chemical, carbon dioxide, or alcohol foam extinguishers. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are selfcontained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positivepressure mode. Disposal Method Suggested: Controlled incineration whereby nitrogen oxides are removed from the effluent gas by scrubber, catalytic or thermal devices.[22]
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Pyriminil
References US Environmental Protection Agency. (April 30, 1980). Pyridine: Health and Environmental Effects Profile No. 150. Washington, DC: Office of Solid Waste New York State Department of Health. (March 1986). Chemical Fact Sheet: Pyridine. Version 2. Albany, NY: Bureau of Toxic Substance Assessment New Jersey Department of Health and Senior Services. (March 2002). Hazardous Substances Fact Sheet: Pyridine. Trenton, NJ
Pyriminil
P:1350
Molecular Formula: C13H12N4O3 Synonyms: DLP787; DPL-87; N-(4-Nitrophenyl)-N0 -(3-pyridinylmethyl)urea; 1-(4-Nitrophenyl)-3-(3-pyridinylmethyl) urea; Priminil; N-3-Pyridylmethyl-N0 ,p-nitrophenylurea; 1(3-Pyridylmethyl)-3-(4-nitrophenyl)urea; Pyridylmethyl-N0 , p-nitrophenylurea; Pyrinuron; RH-787; Urea, N-(4-nitrophenyl)-N0 -(3-pyridinylmethyl)-; Vacor CAS Registry Number: 53558-25-1 RTECS® Number: YI9690000 UN/NA & ERG Number: UN2767/151 EC Number: 258-626-7 Regulatory Authority and Advisory Bodies Superfund/EPCRA 40CFR355, Extremely Hazardous Substances: TPQ 5 100/10,000 lb (45.4/4540 kg). Reportable Quantity (RQ): 100 lb (45.4 kg). European/International Regulations: not listed in Annex 1. WGK (German Aquatic Hazard Class): No value assigned. Description: Pyriminil is a yellow crystalline solid resembling corn meal. Molecular weight 5 272.29; Freezing/ Melting point 5 223 C (decomposition). Hazard Identification (based on NFPA-704 M Rating System): Health 3, Flammability 1, Reactivity 0. Potential Exposure: Those involved in the manufacture, formulation, or application of this single-dose, acute rodenticide. Not registered as a pesticide in the United States. Permissible Exposure Limits in Air Protective Action Criteria (PAC) TEEL-0: 1.25 mg/m3 PAC-1: 3.5 mg/m3 PAC-2: 6.2 mg/m3 PAC-3: 20 mg/m3 Routes of Entry: Inhalation, ingestion, skin and/or eye contact. Harmful Effects and Symptoms Short Term Exposure: This chemical may cause death by cardiovascular collapse and respiratory failure. Symptoms include nausea, vomiting, abdominal pain, chills, mental confusion, anorexia, aching, dilated pupils, dehydration, chest pain, urinary retention, irregular heartbeat, and muscular weakness. Exposure may also result in visual disturbances, central nervous system depression, and tremors.
Long Term Exposure: It may damage the pancreas, causing diabetes. Human survivors regularly develop an insulindeficient, ketosis-prone form of diabetes mellitus. Also, it affects the central nervous system. Points of Attack: Central nervous system. Medical Surveillance: Blood sugar. Examination of the nervous system. First Aid: If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. Keep victim quiet and maintain normal body temperature. Effects may be delayed; keep victim under observation. Personal Protective Methods: Wear protective gloves and clothing to prevent any reasonable probability of skin contact. Safety equipment suppliers/manufacturers can provide recommendations on the most protective glove/clothing material for your operation. All protective clothing (suits, gloves, footwear, headgear) should be clean, available each day, and put on before work. Contact lenses should not be worn when working with this chemical. Wear dust-proof chemical goggles and face shield unless full face-piece respiratory protection is worn. Employees should wash immediately with soap when skin is wet or contaminated. Provide emergency showers and eyewash. Respirator Selection: Follow regulations in OSHA 29CFR1910.134 or European Standard EN149. Use a NIOSH/MSHA- or European Standard EN149-approved respirator; or use an approved supplied-air respirator with a full face-piece operated in the positive-pressure mode, or with a full face-piece, hood, or helmet in the continuousflow mode; or use a NIOSH/MSHA- or European Standard EN149-approved self-contained breathing apparatus with a full face-piece operated in a pressure-demand or other positive-pressure mode. Storage: Color Code—Blue: Health Hazard/Poison: Store in a secure poison location. Prior to working with this chemical you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, wellventilated area. Where possible, automatically transfer material from drums or other storage containers to process containers. Shipping: Phenylurea pesticide, solid, toxic, n.o.s. This compound requires a shipping label of “POISONOUS/ TOXIC MATERIALS.” It falls in Hazard Class 6.1 and Packing Group I.
Pyriminil Spill Handling: Evacuate persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Stay upwind; keep out of low areas. Ventilate closed spaces before entering them. Remove and isolate contaminated clothing at the site. Do not touch spilled material; stop leak if you can do so without risk. Use water spray to reduce vapors. Small spills: absorb with sand or other noncombustible absorbent material and place into containers for later disposal. Small dry spills: with clean shovel place material into clean, dry container and cover; move containers from spill area. Large spills: dike far ahead of spill for later disposal. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your local or federal environmental protection agency for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable. Fire Extinguishing: Poisonous gases are produced in fire, including nitrogen oxides. Small fires: dry chemical, carbon dioxide, water spray, or foam. Large fires: water spray, fog, or foam. Move container from fire area if you can do so without risk. Fight fire from maximum distance. Dike fire control water for later disposal; do not scatter the material. Keep unnecessary people away; isolate hazard area and deny entry. Stay upwind; keep out of low areas. Ventilate closed spaces before entering them. Wear positive pressure
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breathing apparatus and special protective clothing. Remove and isolate contaminated clothing at the site. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode. Disposal Method Suggested: In accordance with 40CFR165, follow recommendations for the disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by contacting your local or federal environmental control agency or by contacting your regional EPA office. References US Environmental Protection Agency. (November 30, 1987). Chemical Hazard Information Profile: Pyriminil. Washington, DC: Chemical Emergency Preparedness Program New Jersey Department of Health and Senior Services. (May 2002). Hazardous Substances Fact Sheet: Pyriminil. Trenton, NJ