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Adsorption of chlorinated pesticides from river water with XAD-2 resin
91
SHORT COMMUNICATIONS
Zusanune~-Die Chelate der seltenen Erden mit Chlorphosphonaxo III werden aus einer wlgrigen Liisung (pH l,l-1,5) leicht in n-Butanol extrahiert. Die Extinktion am Absorptions maximum (bei 668 nm) ist etwa 3-ma1 so grol3 wie die in w5iDriger Liisung. Die spektrophotometrische Bestimmung seltener Erden ist untersucht worden.
Rbsumb-L,es chelates du chlorophosphonazo
III avec les terms rams sont ais6ment extraits d’une solution aqueuse (pH 1,1-1,5) en a-butanol. L’absorbance au maximum d’absorption (a 668 nm) est environ 3 fois celle en solution aqueuse. On a Ctudit le dosage spectrophotometrique des terres rams.
Talnnta, Vol. 21, pp. 91-93.
Per~mmt
Press, 1974. Printed in Great Britain
ADSORPTION OF CHLORINATED PESTICIDES RIVER WATER WITH XAD-2 RESIN
FROM
(Received 26 June 1973. Accepted 3 July 1973)
Usually chlorinated pesticides are present in water in such small amounts that using a separatory funnel to carry out the extraction procedure is difficult because of the large volume of water needed to get meaningful data. For the determination of pesticides at lower concentrations two methods are usually used, continuous extraction with an organic solvent,’ or adsorption on charcoal. ‘* s These two methods are, however, rather time-consuming, requiring one hour to extract 05-l litre of water in the continuous extraction procedure and up to 35 hr extraction with chloroform to recover the pesticide from the charcoal in the charcoal adsorption procedure. Recently several new absorbents have been proposed for the recovery of organics from water. A mixture of Carbowax 4000 monostearate and undecane on a Chromosorb W solid support has been used to recover chlorinated pesticides from water. 4 Amberlite XAD-2 resin has been used to concentrate dissolved organic materials from sea-water.’ Polyurethane foam coated with a selective adsorbent has been used for the extraction of organochlorine pesticides from water.6 Finally Amberlite XAD-2 resin has been used to recover trace organics from potable water. ’ Of these. absorbents, Amberlite XAD-2 resins seemed to have the most potential and Amberlite XAD-2 was evaluated as an absorbent for concentration of trace organochlorine pesticides from river water. EXPERIMENTAL
Apparatus A Beckman GC-5 gas chromatograph the gas chromatography.
equipped with a discharge electron-capture
detector was used for
Column. A 2 x 20 cm glass tube was fitted with a Teflon stop-cock on one end and a T 24140 outer joint on the other. Reservoir. A 5-l. round-bottom flask was fitted with a %24/40 inner joint on the bottom of the flask. A Teflon sleeve was used to seal the joint connecting the reservoir to the column. The XAD-2 resin was supplied by Rohm and Haas Co. The fine particles were removed from the resin by slurrying and decanting several times with water. The resin was filtered off and transferred to a Soxhlet extractor and extracted for 24 hr with pesticide-grade acetonitrile to remove impurities from the resin. The solvent was changed and extraction continued for another 24 hr with fresh solvent. The resin was washed free from acetonitrile with water and stored under water in a glass-stoppered bottle. Procedure A glass-wool plug was placed in the bottom of the column and 10 ml of resin were added to the column in a water slurry. A plug of glass wool was added to the top of the column and the reservoir connected to the top of the column. A 4-1. river-water sample was added to the reservoir and the flow-rate adjusted to approximately 50 ml/min. After the sample had passed through the column, 200 ml of hot acetonitrile were passed through the column at 50 ml/min and collected in a l-l. separatory funnel. Water (700 ml) was
SHORT COMMUNICATIONS
92
added to the separatory funnel and the aqueous acetonitrile was extracted with three 60-ml portions of pesticide-grade petroleum ether (b.p. 30-60”). The combined petroleum ether extracts were washed with two 15-ml portions of water, dried by passing through a column of sodium sulphate and concentrated to 1 ml with a Ku&ma-Danish evaporation assembly and a 3-ball Snyder column. No “ Florisil ” &an-up of the petroleum ether extract was necessary before gas chromatographic analysis. For larger samples a bigger reservoir may be used, or several bottles of river water may be passed through the 5-1. reservoir in succession. RESULTS
AND
DISCUSSION
Table 1 lists the results obtained for a series of weekly samples taken between January and June of 1973 Table 1. Comparison of dieldrin recovery from 4-I. river water samples by the XAD-2 procedure and the regular extraction procedure.* Results given in parts per billion (10”) Date
XAD-2
Jan. 8 Jan. 15 Jan. 24 Feb. 1 Feb. 4 Feb. 11 Feb. 19 March 19 March 24 March 30
Extraction
Date
XAD-2
Extraction
6 13 4 15 16 15 3 2 6 4
April 5 April 15 April 22 April 29 May 6 May 13 May 20 May 28 June 3
4 14 4 2 5 6 4 9 6
4 7 4 : 4 3 9 5
from the Skunk River near Ames, Iowa. The XAD-2 results are the average of duplicate determinations which generally agreed within It1 part per billion (IO”). Die&in was the only pesticide present in sufficient concentration to be monitored accurately with a 4-l. sample. During periods of high run-off or at other times with a larger sample, the following pesticides were detected but not quantitatively: p,p’-DDT, p,p’DDE, p,p’-DDD, o,p’-DDT, heptachlor epoxide, lindane or atrazine or both, and several others yet to be characteri&. The values obtained for dieldrin by using XAD-2 resin compare favourably with those from the regular extraction procedurc.8 The XAD-2 procedure is easier to use in that & 4-l. sample does not have to be manipulated several times. Acknowledgmenr-This Foundation.
project was supported by Grant No. GP-33526X1 from the National Science
JOHNJ. RICHARD JAMESS. FRITZ
Ames Laborarory-USAEC Department of Chemistry Iowa State University Ames, Iowa 50010, U.S.A. REFERENCES
1. L..Kahn and C. H. Wayman, Anal. Chem., 1964.36, 1340. 2. H. A. Rosen and F. M. Middleton, ibid.., 1959, 31, 1729. 3. A. W. Breldenbach, J. J. Lichtenberg. C. F. Henke, D. J. Smith, J. W. Eichelberger, Jr. and H. Stierli, The Iakn~ijkarion and Measurement of Chlorinated Hydrocarbon Pesticides in Surface Water, 1966. Federal Water Quality Administration, No. WP22, Government Printing office, Washington, D.C. 4. B. Ahling and S. Jensen, Anal. Chem., 1970,42, 1483. 5. J. Riley and D. Taylor, AMY. Chim. Acra, 1960, 46, 307. 6. J. F. Uthe, S. Reinke and H. Gesser, EnvironmentalLerters, 1972,3, 117. 7. A. K. Bumham, G. V. Caldar, J. S. Fritz, G. A. Junk, H. J. Svec and R. Willis, Anal. Chem., 1972,44,139. 8. J. J. Lichtenberg, H. Boyle, R. C. Dressman, J. W. Eichelberger, M. Garza, D. Johnson, L. Kahn, J. E. Longbottom. W. Loy, N. Malueg, G. Muth, L. Streck and A. F. Tabri, Methods for Organic Pesricides in Water and Wastewater, 1971. Environmental Protection Agency, Cincinnati, Ohio.
SHORT
COMMUNICATIONS
93
Summary-Pesticides in river water at levels as low as parts per billion (lo”), can be recovered by sorption on a column of XAD-2 resin, followed by elution with acetonitrile. Water is added to the acetonitrile and the pesticides are extracted by petroleum ether and determined by gas chromatography. The new procedure is more convenient to use than the solvent extraction procedure and gives comparable results for dieldrin. Zusammenfassnag-Pestizide in FluBwasser konnen in ppb-Konzentrationen (1012) erfagt werden durch Sorption an einer Saule mit XAD-2-Harz und anschliegender Elution mit Acetonitril. Zum Acetonitril wird Wasser gegeben, die Pestizide mit Petrol&her extrahiert und durch Gaschromatographie bestimmt. Die neue Vorschrift ist bequemer als das Verfahren mit fiiissig-fliissig-Extraktion und dibt bei Dieldrin vergleichbare Erfebnisse. R&sum&On peut recup&er des pesticides dans l’eau de rivibe a des teneurs aussi faibles que des parties par trillion (1012) par sorption sur une colonne de r&sine XAD-2, suivie d’6lution a l’adtonitrile. On ajoute de l’eau a l’acetonitrile et les pesticides sont extraits a l’ether de petrole et determines par chromatographie en phase vapeur. La nouvelle technique est plus commode a utiliser que la technique d’extraction par solvant et donne des resultats comparables pour la dieldrine.
Tahra,
Vol. 21, pp. 93-97. Pergamon Press, 1974. Printed in Great Britain
EXTRACTION-SPECTROPHOTOMETRIC DETERMINATION THALLIUM IN HIGH-PURITY INDIUM
OF
(Received 19 June 1973. Accepted 28 June 1973) An accurate determination of trace quantities of thallium in high-purity indium has great importance in the technology of semi-conductor materials. In the present paper a spectrophotometric method for determining 1O-5-1O-6% thallium in indium is described. High selectivity and sensitivity are attained by extractive separation of thallium from the matrix in hydrochloric acid medium,te5 and determination of thallium as the ion-association complex of TlCL,- with Brilliant Green?-* EXPERIMENTAL
Reagents Spectroscopically pure hydrochloric acid, analytical grade reagents and twice-distilled water were used throughout. Standard thallium solution, 1 mg/ml. Thallium nitrate (1.3650 g) was dissolved in water containing 2 ml of cont. nitric acid and diluted to 1 I. with water. The solution was standardized by precipitation of Tl,CrO., . Working standards were prepared by dilution of this solution. Brilliant Green, 0.01 % solution. Phenol, 10 % solution in glacial acetic acid. Recommended procedure Dissolve a sample of indium (1-5 g) in 25 ml of 6M hydrochloric acid. Add 0.2 g of copper wire and evaporate the solution to about 5 ml. Allow to cool and separate from the copper wire, add 5 ml of 6M hydrochloric acid and 5 drops of bromine water. Add 5 drops of phenol solution and extract thallium with di-isopropyl ether (shaking time 1 min). Wash the organic solution twice with 5-ml portions of 3M hydrochloric acid containing 1 drop of bromine water (shaking time 30 set). Shake the ether extract for 30 set with a mixture of 5 ml of 0.3M hydrochloric acid and 5 ml of Brilliant Green solution. Dilute the extract to volume with di-isopropyl ether in a volumetric flask, measure the absorbance against a blank solution at 630 nm and obtain the thallium concentration from a calibration curve. RESULTS
Determination of thallium with Brilliant Green Thallium complexes
such as TICI,-
or TlBr,-
and Brilliant Green form an ion-association
complex,
SHORT COMMUNICATIONS
Zusanune~-Die Chelate der seltenen Erden mit Chlorphosphonaxo III werden aus einer wlgrigen Liisung (pH l,l-1,5) leicht in n-Butanol extrahiert. Die Extinktion am Absorptions maximum (bei 668 nm) ist etwa 3-ma1 so grol3 wie die in w5iDriger Liisung. Die spektrophotometrische Bestimmung seltener Erden ist untersucht worden.
Rbsumb-L,es chelates du chlorophosphonazo
III avec les terms rams sont ais6ment extraits d’une solution aqueuse (pH 1,1-1,5) en a-butanol. L’absorbance au maximum d’absorption (a 668 nm) est environ 3 fois celle en solution aqueuse. On a Ctudit le dosage spectrophotometrique des terres rams.
Talnnta, Vol. 21, pp. 91-93.
Per~mmt
Press, 1974. Printed in Great Britain
ADSORPTION OF CHLORINATED PESTICIDES RIVER WATER WITH XAD-2 RESIN
FROM
(Received 26 June 1973. Accepted 3 July 1973)
Usually chlorinated pesticides are present in water in such small amounts that using a separatory funnel to carry out the extraction procedure is difficult because of the large volume of water needed to get meaningful data. For the determination of pesticides at lower concentrations two methods are usually used, continuous extraction with an organic solvent,’ or adsorption on charcoal. ‘* s These two methods are, however, rather time-consuming, requiring one hour to extract 05-l litre of water in the continuous extraction procedure and up to 35 hr extraction with chloroform to recover the pesticide from the charcoal in the charcoal adsorption procedure. Recently several new absorbents have been proposed for the recovery of organics from water. A mixture of Carbowax 4000 monostearate and undecane on a Chromosorb W solid support has been used to recover chlorinated pesticides from water. 4 Amberlite XAD-2 resin has been used to concentrate dissolved organic materials from sea-water.’ Polyurethane foam coated with a selective adsorbent has been used for the extraction of organochlorine pesticides from water.6 Finally Amberlite XAD-2 resin has been used to recover trace organics from potable water. ’ Of these. absorbents, Amberlite XAD-2 resins seemed to have the most potential and Amberlite XAD-2 was evaluated as an absorbent for concentration of trace organochlorine pesticides from river water. EXPERIMENTAL
Apparatus A Beckman GC-5 gas chromatograph the gas chromatography.
equipped with a discharge electron-capture
detector was used for
Column. A 2 x 20 cm glass tube was fitted with a Teflon stop-cock on one end and a T 24140 outer joint on the other. Reservoir. A 5-l. round-bottom flask was fitted with a %24/40 inner joint on the bottom of the flask. A Teflon sleeve was used to seal the joint connecting the reservoir to the column. The XAD-2 resin was supplied by Rohm and Haas Co. The fine particles were removed from the resin by slurrying and decanting several times with water. The resin was filtered off and transferred to a Soxhlet extractor and extracted for 24 hr with pesticide-grade acetonitrile to remove impurities from the resin. The solvent was changed and extraction continued for another 24 hr with fresh solvent. The resin was washed free from acetonitrile with water and stored under water in a glass-stoppered bottle. Procedure A glass-wool plug was placed in the bottom of the column and 10 ml of resin were added to the column in a water slurry. A plug of glass wool was added to the top of the column and the reservoir connected to the top of the column. A 4-1. river-water sample was added to the reservoir and the flow-rate adjusted to approximately 50 ml/min. After the sample had passed through the column, 200 ml of hot acetonitrile were passed through the column at 50 ml/min and collected in a l-l. separatory funnel. Water (700 ml) was
SHORT COMMUNICATIONS
92
added to the separatory funnel and the aqueous acetonitrile was extracted with three 60-ml portions of pesticide-grade petroleum ether (b.p. 30-60”). The combined petroleum ether extracts were washed with two 15-ml portions of water, dried by passing through a column of sodium sulphate and concentrated to 1 ml with a Ku&ma-Danish evaporation assembly and a 3-ball Snyder column. No “ Florisil ” &an-up of the petroleum ether extract was necessary before gas chromatographic analysis. For larger samples a bigger reservoir may be used, or several bottles of river water may be passed through the 5-1. reservoir in succession. RESULTS
AND
DISCUSSION
Table 1 lists the results obtained for a series of weekly samples taken between January and June of 1973 Table 1. Comparison of dieldrin recovery from 4-I. river water samples by the XAD-2 procedure and the regular extraction procedure.* Results given in parts per billion (10”) Date
XAD-2
Jan. 8 Jan. 15 Jan. 24 Feb. 1 Feb. 4 Feb. 11 Feb. 19 March 19 March 24 March 30
Extraction
Date
XAD-2
Extraction
6 13 4 15 16 15 3 2 6 4
April 5 April 15 April 22 April 29 May 6 May 13 May 20 May 28 June 3
4 14 4 2 5 6 4 9 6
4 7 4 : 4 3 9 5
from the Skunk River near Ames, Iowa. The XAD-2 results are the average of duplicate determinations which generally agreed within It1 part per billion (IO”). Die&in was the only pesticide present in sufficient concentration to be monitored accurately with a 4-l. sample. During periods of high run-off or at other times with a larger sample, the following pesticides were detected but not quantitatively: p,p’-DDT, p,p’DDE, p,p’-DDD, o,p’-DDT, heptachlor epoxide, lindane or atrazine or both, and several others yet to be characteri&. The values obtained for dieldrin by using XAD-2 resin compare favourably with those from the regular extraction procedurc.8 The XAD-2 procedure is easier to use in that & 4-l. sample does not have to be manipulated several times. Acknowledgmenr-This Foundation.
project was supported by Grant No. GP-33526X1 from the National Science
JOHNJ. RICHARD JAMESS. FRITZ
Ames Laborarory-USAEC Department of Chemistry Iowa State University Ames, Iowa 50010, U.S.A. REFERENCES
1. L..Kahn and C. H. Wayman, Anal. Chem., 1964.36, 1340. 2. H. A. Rosen and F. M. Middleton, ibid.., 1959, 31, 1729. 3. A. W. Breldenbach, J. J. Lichtenberg. C. F. Henke, D. J. Smith, J. W. Eichelberger, Jr. and H. Stierli, The Iakn~ijkarion and Measurement of Chlorinated Hydrocarbon Pesticides in Surface Water, 1966. Federal Water Quality Administration, No. WP22, Government Printing office, Washington, D.C. 4. B. Ahling and S. Jensen, Anal. Chem., 1970,42, 1483. 5. J. Riley and D. Taylor, AMY. Chim. Acra, 1960, 46, 307. 6. J. F. Uthe, S. Reinke and H. Gesser, EnvironmentalLerters, 1972,3, 117. 7. A. K. Bumham, G. V. Caldar, J. S. Fritz, G. A. Junk, H. J. Svec and R. Willis, Anal. Chem., 1972,44,139. 8. J. J. Lichtenberg, H. Boyle, R. C. Dressman, J. W. Eichelberger, M. Garza, D. Johnson, L. Kahn, J. E. Longbottom. W. Loy, N. Malueg, G. Muth, L. Streck and A. F. Tabri, Methods for Organic Pesricides in Water and Wastewater, 1971. Environmental Protection Agency, Cincinnati, Ohio.
SHORT
COMMUNICATIONS
93
Summary-Pesticides in river water at levels as low as parts per billion (lo”), can be recovered by sorption on a column of XAD-2 resin, followed by elution with acetonitrile. Water is added to the acetonitrile and the pesticides are extracted by petroleum ether and determined by gas chromatography. The new procedure is more convenient to use than the solvent extraction procedure and gives comparable results for dieldrin. Zusammenfassnag-Pestizide in FluBwasser konnen in ppb-Konzentrationen (1012) erfagt werden durch Sorption an einer Saule mit XAD-2-Harz und anschliegender Elution mit Acetonitril. Zum Acetonitril wird Wasser gegeben, die Pestizide mit Petrol&her extrahiert und durch Gaschromatographie bestimmt. Die neue Vorschrift ist bequemer als das Verfahren mit fiiissig-fliissig-Extraktion und dibt bei Dieldrin vergleichbare Erfebnisse. R&sum&On peut recup&er des pesticides dans l’eau de rivibe a des teneurs aussi faibles que des parties par trillion (1012) par sorption sur une colonne de r&sine XAD-2, suivie d’6lution a l’adtonitrile. On ajoute de l’eau a l’acetonitrile et les pesticides sont extraits a l’ether de petrole et determines par chromatographie en phase vapeur. La nouvelle technique est plus commode a utiliser que la technique d’extraction par solvant et donne des resultats comparables pour la dieldrine.
Tahra,
Vol. 21, pp. 93-97. Pergamon Press, 1974. Printed in Great Britain
EXTRACTION-SPECTROPHOTOMETRIC DETERMINATION THALLIUM IN HIGH-PURITY INDIUM
OF
(Received 19 June 1973. Accepted 28 June 1973) An accurate determination of trace quantities of thallium in high-purity indium has great importance in the technology of semi-conductor materials. In the present paper a spectrophotometric method for determining 1O-5-1O-6% thallium in indium is described. High selectivity and sensitivity are attained by extractive separation of thallium from the matrix in hydrochloric acid medium,te5 and determination of thallium as the ion-association complex of TlCL,- with Brilliant Green?-* EXPERIMENTAL
Reagents Spectroscopically pure hydrochloric acid, analytical grade reagents and twice-distilled water were used throughout. Standard thallium solution, 1 mg/ml. Thallium nitrate (1.3650 g) was dissolved in water containing 2 ml of cont. nitric acid and diluted to 1 I. with water. The solution was standardized by precipitation of Tl,CrO., . Working standards were prepared by dilution of this solution. Brilliant Green, 0.01 % solution. Phenol, 10 % solution in glacial acetic acid. Recommended procedure Dissolve a sample of indium (1-5 g) in 25 ml of 6M hydrochloric acid. Add 0.2 g of copper wire and evaporate the solution to about 5 ml. Allow to cool and separate from the copper wire, add 5 ml of 6M hydrochloric acid and 5 drops of bromine water. Add 5 drops of phenol solution and extract thallium with di-isopropyl ether (shaking time 1 min). Wash the organic solution twice with 5-ml portions of 3M hydrochloric acid containing 1 drop of bromine water (shaking time 30 set). Shake the ether extract for 30 set with a mixture of 5 ml of 0.3M hydrochloric acid and 5 ml of Brilliant Green solution. Dilute the extract to volume with di-isopropyl ether in a volumetric flask, measure the absorbance against a blank solution at 630 nm and obtain the thallium concentration from a calibration curve. RESULTS
Determination of thallium with Brilliant Green Thallium complexes
such as TICI,-
or TlBr,-
and Brilliant Green form an ion-association
complex,