Dermal Toxicity Testing see Toxicity Testing, Dermal Desferrioxamine see Deferoxamine Desipramine see Tricyclic Antidepressants
Detergent Z Cai, University of Louisiana at Monroe, Monroe, LA, USA PJ Hakkinen, Institute for Health and Consumer Protection, Ispra, Italy Ó 2014 Elsevier Inc. All rights reserved. This article is a reprint from the previous edition, volume 1, pp 739–742, Ó 2005, Elsevier Inc.
Detergents are various surface-active agents (surfactants) particularly effective in dislodging foreign matter from soiled surfaces and retaining it in suspension. Soap, which is made from fats or fatty acids, is a detergent. However, in common usage the term ‘detergent’ applies to the synthetic nonsoap substances, not to soap, and also to products made from synthetic surfactants. Surfactants and builders are the major components of cleaning products, with the builders serving to enhance or maintain the cleaning efficiency of the surfactants, primarily by reducing the hardness in water. Other ingredients are added to formulations to provide functions such as increasing cleaning performance for specific soils/surfaces, ensuring product stability, and supplying a unique identity to a product. Examples include foam stabilizers, optical brighteners or whiteners, antiredeposition agents, bleaching agents (chlorine-releasing agents) or bactericidal agents (mild concentrations of quaternary ammonium compounds), enzymes, fragrances, and dyes. Water is likely to be the major component of a liquid version of a detergent product. Soaps and detergents are important for personal and public health. The (US) Soap and Detergent Association has noted that, through their ability to loosen and remove soil from a surface, soaps and detergents can (1) contribute to good personal hygiene, (2) reduce the presence of germs that cause infectious diseases, and (3) extend the useful life of clothes, tableware, linens, surfaces, and furnishings. Soaps and detergents found in the home can be grouped into four general categories: personal cleansing, laundry, dishwashing, and household cleaning. The surfactants used in detergents have been developed to perform well under a variety of conditions and are less sensitive than soap to the hardness minerals in water. Most surfactants will not form a film. Detergent surfactants were developed in response to a shortage of animal and vegetable fats and oils during World War I and World War II. In addition, a substance that was able to perform in hard water was desired to make cleaning more effective. Petroleum was used for the manufacture of these initial surfactants since it was widely available; however, detergent surfactants are now made from a variety of
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petrochemicals (derived from petroleum) and/or oleochemicals (derived from fats and oils). Surfactants are usually classified by their ionic properties in water. Anionic surfactants are used in laundry and hand dishwashing detergents, household cleaners, and personal cleansing products. Linear alkylbenzene sulfonate, alcohol ethoxysulfates, alkyl sulfates, and soap are common anionic surfactants. Nonionic surfactants are low sudsing and are typically used in laundry and automatic dishwasher detergents and rinse aids. The most widely used nonionic surfactants are alcohol ethoxylates. Cationic surfactants are used in fabric softeners and in fabric-softening laundry detergents. Other cationics are the disinfecting/sanitizing ingredients used in some household cleaners. Quaternary ammonium compounds are the major cationic surfactants. Amphoteric surfactants are used in personal cleansing and household cleaning products for their mildness, sudsing, and stability. Imidazolines and betaines are major amphoteric surfactants. Even the different product types within a category of detergents are formulated in different product forms and with different ingredients selected to meet consumer desires for a selection of product types, to perform a broad cleaning function, and to deliver properties specific to that product. For example, laundry detergents and laundry aids are available as liquids, powders, gels, sticks, sprays, pumps, sheets, and bars. They have been formulated to meet a variety of soil and stain removal, bleaching, fabric softening and conditioning, and disinfectant needs under varying conditions of water, temperature, and use. Further, the laundry detergents are either general purpose or light duty, with general-purpose detergents being suitable for all washable fabrics, and liquids working best on oily soils, and for pretreating soils and stains. Light-duty detergents are used for hand or machine washing lightly soiled items and delicate fabrics. Water alone will not remove oily, greasy soil on clothing since the oil and grease repel the water molecules; however, a surfactant’s hydrophobic end is attracted to the oil and the hydrophilic end is attracted to the water molecules. These opposing forces loosen the soil and suspend it in the water. Warm or hot water helps dissolve grease and oil in soil. The
Encyclopedia of Toxicology, Volume 2
http://dx.doi.org/10.1016/B978-0-12-386454-3.00487-5
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agitation of the water and clothing in a washing machine, or rubbing clothing with the hands or an implement helps to pull the soil free from the clothing. Exposure and risk assessors and the developers of consumer products need to understand the reasonably foreseeable ways that consumers will use the products. Even a task as simple as dispensing a laundry detergent powder from its box into the washing machine could be done in several different ways by a consumer, resulting in different types and magnitudes of potential exposures. For example, the laundry powder could be poured from different heights above the washing machine, directly into the washing machine from the box, from the box into a measuring cup, etc. These and other possible differences in just how the product is dispensed could lead to meaningful differences in the types and magnitudes of inhalation and skin exposures to the powder. Further, exposure and risk assessors and the developers of consumer products need to understand the reasonably foreseeable ways that consumers will use a product in combination with other products. For example, laundry detergents are often used in combination with other products that might be useful for particular needs. For example, laundry aids contribute to the effectiveness of laundry detergents and provide special functions. Boosters enhance the soil and stain removal, brightening, buffering, and water softening performance of detergents and are used in the washing machine in addition to the detergent. Enzyme presoaks are used for soaking items before washing to remove difficult stains and soils. Fabric softeners are added to the final rinse as a liquid or to the clothes dryer on a nonwoven sheet. Prewash soil and stain removers are used to pretreat heavily soiled and stained garments. Starches, fabric finishes, and sizings are used in the final rinse or after drying. Water softeners are added to the wash or rinse to inactivate hard water minerals and increase cleaning power since detergents are more effective in soft water. Bleaches (chlorine and oxygen) are used to whiten and brighten fabrics and help remove stubborn stains, and liquid chlorine bleach (e.g., a sodium hypochlorite solution) can disinfect and deodorize fabrics. In addition to laundry products, detergents are used in dishwashing products for hand and machine dishwashing. They are available as liquids, gels, powders, and solids. Further, many types of household cleaning products are available for consumers because no single cleaning product can provide optimum performance on all surfaces and soils. Thus, a broad range of products has been formulated to clean efficiently and easily, including liquids, gels, powders, solids, sheets, and pads for use on painted, plastic, metal, porcelain, glass, and other surfaces and on washable floor coverings.
Human Safety Human safety evaluations begin with the specific ingredients, and then move on to the whole product. The effects of all ingredients are considered as the product is formulated. Human safety-related data for a chemical used in a detergent or soap product (or in another type of consumer product), and for an entire formulation, can come from in silico data (from computer programs that estimate toxic properties
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based on data for similar chemicals and/or from the physical and chemical properties of the chemical of interest), in vitro data (from the results of ‘alternatives to animal’ tests, e.g., from cell cultures used to assess eye or skin irritation potential), animal (toxicological) studies (e.g., to assess eye or skin irritation potential), and human data (examples are discussed below). The human data include premarketing (i.e., before a product has begun to be sold to consumers) clinical and ‘controlled use’ studies of the entire formulation. Further, the human data could include postmarketing (i.e., after a product has begun to be sold to consumers) studies conducted by physicians or dermatologists and epidemiological studies developed by poison control centers, companies, academia, etc. Examples of human testing that may be very useful in the safety evaluation of detergents and other consumer products include human clinical studies, e.g., patch tests to confirm the absence of meaningful human skin irritation potential predicted from in vitro and any animal studies. Possible human studies also include ‘controlled use’ studies, e.g., from studies designed to assess the skin effects from wearing a type of fabric laundered with a new detergent formula. Further, examinations of the ‘real-world’ experiences consumers have had using a product are very helpful in confirming the absence of meaningful safety issues or could lead to changes in product composition, labeling, package design, etc., if the risk assessor judges that the data indicate a need to refine the product to lower risks. As noted above, these real-world data can come from human epidemiological studies and other studies developed by poison control centers, companies, academia, and others to look at the health effects associated with the use of a consumer product under reasonably foreseeable conditions. Even though manufacturers formulate and package their cleaning products to ensure that they are safe or have very low risk, human health effects can still result from normal uses and unintended exposures. To warn consumers about a specific hazard, household cleaning products carry cautionary labeling whenever necessary, e.g., CAUTION, WARNING, or DANGER, along with first aid instructions. A laundry product label might look like: Caution. Eye irritant. Harmful if swallowed. KEEP OUT OF REACH OF CHILDREN. If swallowed, give a glassful of water. Call a physician. In case of eye contact, flush with water. The manufacturer’s safety data and material safety data sheet supporting this labeling might indicate the following: Acute Health Effects Inhalation: Transient irritation with prolonged exposure to concentrated material. Ingestion: May result in nausea, vomiting, and/or diarrhea. Eye Contact: May cause stinging, tearing, itching, swelling, and/or redness. Skin: Prolonged contact with concentrated material may be drying or transiently irritating to skin. In addition, companies, marketing detergents, soaps, and other products tend to work closely with poison control centers to assure that, should an accidental exposure occur, treatment information is available to health care providers and concerned parents.
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While most laundry detergents are not strong enough to do significant harm, some laundry products, automatic dishwashing detergents, wall cleaners, drain or oven cleaners, disinfectants, and ammonia can cause extensive injury. In addition, extensive eye and skin exposure to some detergents may also cause toxic effects. Further, product interactions might occur. For example, the mixing of a toilet bowl cleaner or any acid with a chlorine-type bleach may produce chlorine gas, causing respiratory irritation with coughing, labored breathing, and inflammation of the eyes and mucous membranes, and the addition of ammonia to bleach produces a toxic gas, chloramine. As the title of one risk communication book states, ‘Read the label,’ especially if the product is a new one for a consumer.
Occupational Safety Occupational allergy and occupational asthma were safety issues many years ago with the manufacture of detergents. However, comprehensive preclinical, clinical, and industrial hygiene programs have been developed to successfully control allergy and asthma to enzymes used in the detergent industry. The detergent industry has developed guidelines for the safety assessment of enzymes, control of exposure to enzymes, and medical surveillance of enzyme-exposed workers, and occupational allergy and asthma to enzymes in the detergent industry have become uncommon. The cases that have been documented in some manufacturing sites have had poor adherence to the guidelines. Those manufacturing sites that have adhered to the guidelines have had few cases of allergy and asthma to enzymes among exposed workers. Further, reviews of medical data from these sites have shown that workers who have developed IgE antibody to enzymes can continue to work with enzymes and remain symptom free. The basic principles of these programs can be applied to other industries where occupational allergy and asthma to proteins are safety issues.
Environmental Safety Most household cleaning products are formulated to be used with water and ‘go down the drain’ into wastewater treatment systems (municipal sewage treatment plants or septic tank systems). To ensure that these types of products are safe for the environment, manufacturers evaluate the impacts of product ingredients in wastewater treatment systems, streams, rivers, lakes, and estuaries. Environmental risk assessment considers the exposure concentrations and effects of individual ingredients. Two sets of information are used in these assessments. One set enables industry scientists to predict the concentration of the ingredient from all sources, including cleaning products, at various locations in the environment (the predicted exposure concentration). The other set is used to find the highest concentration of the ingredient at which no harm will occur to animals, plants, or microorganisms living in the environment, i.e., the predicted no-effect concentration. Comparing the predicted exposure concentration and the predicted no-effect
concentration enables scientists to determine whether the use of an ingredient is safe for the environment. An example of an environment issue for detergents is the finding that high levels of phosphates in detergents discharged into water systems can lead to a buildup of nutrients that results in a large amount of algae and water plant growth (a complex process called eutrophication). Public, academic, and government concerns have led to adverse publicity, to legislation banning the use of phosphate detergents, and to the development of nonphosphate versions of products.
Environmental Quality The (US) Soap and Detergent Association has noted that manufacturers of cleaning products have been leaders in reducing packaging waste and encouraging sound waste disposal practices. For example, “Advances in technology have resulted in products that are more concentrated, products that combine two functions in one, products with refill packages and packages that use recycled materials. Concentrated products need less energy to manufacture and transport and require less packaging. Multifunctional products eliminate the need for separate packages. Refill packages allow consumers to reuse primary packages many times, decreasing the amount of packaging used and the volume of trash generated. Plastic and paperboard that would otherwise be thrown away become usable materials through recycling.” Finally, life cycle assessment (LCA) is being used to improve the environmental quality of detergents. LCA provides a ‘cradle-to-grave’ or ‘cradle-to-cradle’ evaluation of the environmental impacts of a product and its package, usually all the way from acquiring the raw materials, manufacture and distribution, and consumer usage and disposal. The use of LCA can help assess whether reducing an environmental impact in one area, e.g., manufacturing, moves the impact to disposal or another area. LCA also helps highlight where environmental improvement efforts should be focused.
See also: Alkalies; Recalls, Drugs and Consumer Products; Consumer Product Safety Commission; Recommended Exposure Limits; Occupational Exposure Limits; Ecological Exposure Limits and Guidelines; Environmental Life Cycle Assessment; Poisoning Emergencies in Humans; Surfactants, Anionic and Nonionic.
Further Reading Azizullah, A., Richter, P., Häder, D.P., September 2011. Toxicity assessment of a common laundry detergent using the freshwater flagellate Euglena gracilis. Chemosphere 84 (10), 1392–1400. Basketter, D., Berg, N., Kruszewski, F.H., Sarlo, K., Concoby, B., 2012. Relevance of sensitization to occupational allergy and asthma in the detergent industry. J. Immunotoxicol. 9 (3), 314–319. Basketter, D., Berg, N., Kruszewski, F.H., Sarlo, K., Concoby, B., July–September 2012. The toxicology and immunology of detergent enzymes. J. Immunotoxicol. 9 (3), 320–326. Bello, A., Quinn, M.M., Perry, M.J., Milton, D.K., 2010. Quantitative assessment of airborne exposures generated during common cleaning tasks: a pilot study. Environ. Health 9, 76.
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Felter, S.P., Ryan, C.A., Basketter, D.A., Gilmour, N.J., 2003. Application of the risk assessment paradigm to the induction of allergic contact dermatitis. Regul. Toxicol. Pharmacol. 37, 1–10. Quirce, S., Barranco, P., 2010. Cleaning agents and asthma. J. Investig. Allergol. Clin. Immunol. 20 (7), 542–550. Roggeband, R., York, M., Pericoi, M., Braun, W., 2000. Eye irritation responses in rabbit and man after single applications of equal volumes of undiluted model liquid detergent products. Food Chem. Toxicol. 38, 727–734. Sarlo, K., 2003. Control of occupational asthma and allergy in the detergent industry. Ann. Allergy Asthma Immunol. 90, 32–34. Schneir, A.B., Rentmeester, L., Clark, R.F., Cantrell, F.L., June 2013. Toxicity following laundry detergent pod ingestion. Pediatr. Emerg. Care 29 (6), 741–742.
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Relevant Websites http://ec.europa.eu/enterprise/sectors/chemicals/documents/specific-chemicals/ detergents/ – (EU) European Commission DG Enterprise and Industry. Detergents. http://www.aise.eu/ – (EU) International Association for Soaps, Detergents and Maintenance Products. http://www.heraproject.com – The Human and Environmental Risk Assessment (HERA) Project. http://hpd.nlm.nih.gov – (US) National Library of Medicine, Household Products Database. http://toxtown.nlm.nih.gov – (US) National Library of Medicine, ToxTown. http://www.cleaninginstitute.org – American Cleaning Institute.