Concentrating organics in water for biological testing - ACS Publications

water for biological testing. Many methods are described in the literature but no single method is adequate for concentrating all organics in water sa...
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Concentrating organics in water for biological testing Many methods are described in the literature but no single method is adequate for concentrating all organics in water samples; each has its advantages and disadvantages Robert L. Jolley Oak Ridge Nalional Laboratory Oak Ridge, Tenn. 37830

Before trace amounts of organic constituents that are in aqueous solutions as complex mixtures can be analyzed, the solutions must be concentrated. This is necessary so that a sufficient mass of organics can be obtained for separation and subsequent identitisation. An analogous situation exists for determining the biological activity of such unknown or mostly unknown trace organic constituents in waters of environmental or public health concern. This is especially true for biological testing of long duration or testing that requires many large test species. For instance, a long-term feeding study of mice could require organic material from many thousands of liters of water. Procedures which combine several techniques have been developed to achieve the highest possible recovery of organics. Nevertheless, there are still critical areas, including changes in organic residues that can occur between preparation of the concentrates and biological testing or chemical analysis. The choice of method or combination of methods for concentration is dependent on such factors as the volatility of the organic constituent to be tested, the degree of concentration required, and the biological test system to be used. Kopfler (l980a) divides concentration methods into two basic categories: I . concentration-those processes in which water is removed and the dissolved substances are left behind. Examples are freeze concentration, lyophilization (freeze drying), vacuum distillation, and membrane processes such as reverse osmosis and ultrafiltration. A common disadvantage to 874

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these methods is that inorganic species are concentrated along with the organic constituents. 2. isolation-those processes in which the organic substances are removed from the water. Examples are solvent extraction and adsorption on activated carbon and resins. Concentration techniques In the freeze concentration process, a portion of the water sample is frozen, which concentrates the dissolved substances in the unfrozen portion (Shapiro, 1961; Baker, 1967a, 1967b, 1969, 1970; Mallevialle, 1972). In this process, Baker demonstrated 80% recovery of m-cresol (initial concentration, 310 ppm) with a 20-fold volume reduction. Generally, recovery of organic constituents decreased with increasing inorganic concentration. The method was laboratory-tested for milliliter volumes. Commercial equipment is not currently available. In lyophilization, or the freezedrying process, the water sample is frozen and the water is removed by sublimation under vacuum. The more-volatile organic constituents are lost in this process. Concentration factors of several thousand can be achieved and are limited by recovery of the organics from the residue, which

is composed largely of inorganic salts. Commercial lyophilizers are capable of processing many liters of water per day. This process has been used to prepare concentrates for chemical analysis and biological testing. A major disadvantage is the difficulty of recovering the organic material from the inorganic precipitates (Jolley et al., 1979: Cumming et al., 1979). In the vacuum distillation or evaporation process, the water sample is boiled at reduced pressure and at ambient or near-ambient temperature. This process has been used to concentrate water samples for chemical analysis and for determination of biological activity (Jolley et al., 1975; Johnston and Verdeyen, in press). This process has essentially the same disadvantages as the lyophilization process; however, vacuum distillation is usually more labor-intensive than lyophilization. Laboratory-scale equipment is limited to sample volumes of several liters per day. I n the reverse-osmosis process, water is forced through a membrane by application of pressure greater than the osmotic pressure across the membrane, thereby enriching the water sample in constituents that ordinarily cannot pass through the membrane. Commercial units capable of handling many liters per day are available. The membrane is generally either cellulose acetate or nylon. A disadvantage of reverse osmosis is that the membranes may either adsorb constituents or release contaminants into the sample. Cellulose acetate membranes for reverse osmosis are commonly rated to reject 90-97% of the inorganic ions and organic constituents with molecular weights >200. This process has been used to prepare water samples for chemical analyses and for determination of biological activity (Kopfler, 1980a; Tardiff et al., 1978; Kopfler et al., 1975; Kopfler et al., 1977). Approxi-

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mately 30-40% of organics are recovered from tap water when solvent extraction and dialysis are used in combination with reverse osmosis (Kopfler et al., 1975). Kopfler et al. (1977) reported that cellulose acetate membranes rejected -85% of the total organic carbon from Cincinnati, Ohio, drinking water. In the ultrafiltration process, a water sample is filtered under pressure through a membrane that will pass molecular constituents below a certain size (e.g., 1000 mol wt) and retain those above that size. This technique has been used to concentrate highermolecular-weight constituents for chemical analysis (Milanovich et al., 1975; Macko et al., 1979; McCahill et al., 1980). An obvious disadvantage is the loss of lower-molecular-weight constituents. Commercial units capable of filtering liter quantities per day areavailable. Milanovich et al. (1975) indicated good recoveries of organic constituents by both ultrafiltration and lyophilization, but ultrafiltration is superior for recovery of humic materials. Pope (1980) reported that a high concentration of salt occurred in the retentates from a series of experiments in which vacuum distillation was used for preconcentration.

In the activated-carbon process, the water sample is passed through a column of activated carbon and the adsorbed organic constituents are subsequently eluted with a suitable solvent. The activated-carbon adsorption process has been developed extensively over several decades (Braus et al., 1951;Rosen. 1976;Suffetetal.. 1978).

It has been the principal choice for chemical analysls in the past and is used as a standard method for water analysis (Standard Methods, 1976). Activated-carbon samplers have been developed that can process many thousands of gallons (Middleton et al., 1962). A major disadvantage of the processisthatrecoveryoftheadsorbed

Isolation techniques Solvent extraction of water with immiscible organic solvents has long been a unit process of considerable significance to the chemical industry. According to Kopfler (1980a). direct liquid-liquid extraction is suitable for recovery of organics from liter volumes of water, but continuous extractors are recommended for large volumes. Continuous liquid-liquid extractors in this size range are commercially available. Suffet et al. (1976) report the use of continuous liquid-liquid extractors to remove organics from drinking water supplies. Kopfler (1980a) indicates that impurities present in solvents can be concentrated along with sample constituents; for example, cyclohexene, which is present in the best grades of methylene chloride solvent, is concentrated with the extracted organics when the solvent is distilled off. He also cited the possibility that peroxide contaminants in ether may react with sample components. Another major disadvantage of solvent extraction is specificity. Organic solvents and extraction parameters (e.g., pH, ionic strength, and temperature) must be tailored to accommodate the chemistry of the material to be extracted. Volume 15. Number 8, August 1981

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organics is not complete. The usual recovery process is to air-dry the carbon and use a prolonged Soxhlet extraction with chloroform and then ethanol (Kopfler, 1980a). Supercritical liquid carbon dioxide is being evaluated as a solvent for organics adsorbed on activated carbon (Modell et al., 1980). Fuchs and Kuhn (1975) studied the relative eificacy of solvents for removine adsorbed oreanicr from activated-carbon filters used to treat drinking water. They determined the following yields (grams of organic residue per kilogram of activated carbon): chloroform, 2.5; dioxane, 4.4; ethanol, 9.6; acetone, 10.9; dimethylformamide, 29.7. Fuchs and Kuhn recommend sequential use of dioxane and dimethylformamide for recovery of organics from activated carbon. Carbonaceous adsorbents, or carbonized resins in the form of hard, nondusting spheres (20-50 mesh), are a class of recently developed synthetic adsorbents with a composition between activated carbon and polymeric adsorbents. The chemical structure, surface properties, and pore-size distribution of these adsorbents can be varied to enhance adsorption of nonpolar organics (e.g., chloroform) or more-polar organics (e&, phenol). Carbonized adsorbents have adsorp tion capacities similar to activated carbon (Denton et al., 1980; Suffet et al., 1978 [activated carbon]) and so have potential as an isolation method for organic constituents; however, more information is necessary for evaluation of their adsorption and desorption properties. The adsorption on XAD resins of organic components in aqueous solutions has been studied extensively. Two types of XAD resins (produced by Rohm and Haas) are available: a series that is essentially styrene-divinylbenzene copolymers, and an acrylic ester polymer (Kopfler, 1980a; Dressler, 1979; Junk et al., 1974). These resins have macroreticular characteristics and high sorptive capacity. One disadvantage is that the resins must be exhaustively extracted prior to use to remove contaminants. For example, XAD-2 resins are prepared for chromatographic use by serial extraction of the resin with methanol, diethyl ether, and acetonitrile in a Soxhlet extractor. Clean resins must be stored under methanol and, prior to use, must be evaluated to ensure that resin contaminants are minimal during chromatography. XAD resins have been used to isolate organic constituents for chemical analysis and determination of biological activity. The styrene-divinylben876

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zene series (e.g., XAD-2) has a high affinity for nonpolar (hydrophobic) constituents (Junk et al., 1974), However, these resins are limited in retention capacity for polar constituents. The macroreticular, nonionk, acrylic ester polymer (e&, XAD-8) is much more efficient than XAD-2 in the recovery of polar (hydrophilic) components-such as humic-substances [Thurman et al.. 1978). . Adsorption optimization generally requires pH adjustment and control of flow rates. Malcolm et al. (1977.1980) estimate that about 50% of the total organic carbon of the average water sample can be concentrated on an XAD-8 resin column.

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Adsorbed organic constituents are recovered by elution with organic solvents or, in the case of ionizable substances, by elution with aqueous acidic or basic solutions. In the latter case, although a more concentrated aqueous solution is obtained than in the original water sample, further concentration may be necessary for biological testing. A variety of organic solvents are used for eluting adsorbed neutral organic constituents (e.&, diethyl ether, methanol, acetone, and methylene chloride). As in the case of activated carbon, all adsorbed organic substances are not recoverable from the resin. For example, Aiken et al. (1979) indicated that about 20% of the humic substances bind irreversibly to XAD-2 resin after adsorprion at pH 2 and cannot be eluted with either alkali or organic solvents. Open-pore polyurethane, a recently developed in-situ polymerized resin, has high adsorption capacity for phenols, polycyclic aromatic hydrocarbons, primary amines, and nitrogencontaining heterocyclic compounds. On a weight sorbent basis, open-pare polyurethane capacity is approximately equivalent to that of activated charcoal. The adsorbed organics are

easily and efficiently removed from the resin by suitable solvents. In-situ resin polymerization is readily adaptable to large-scale use (Denton et al., 1980; Denton and Dinsmore, 1980). Although of promising potential for water treatment, more information is necessary before an evaluation can be made of open-pore polyurethane use for concenking organics in water for biological tcstina. esDeciallv in the area of resin “bleed.;’ . Ion-exchange chromatography is useful for separating a large variety of organic constituents (e& amino acids, carbohydrates, and nucleotides) from complex mixtures in aqueous solutions (Scott, 1971). Using strongly basic anion-exchange resin, Junk and Richard (1980) achieved an average recovery efficiency of 90% for 50 compounds in distilled water solution. These included aliphatic acids; chloroand nitroDhenols: substituted ahhatic. aromati;, sulfonic, and phoiphoric acids; and neutral compounds. Nearly 100% recovery was obtained for 140-mg/L (40 ppm) solutions of 2,4dichlorophenoxyacetic acid and tetrachloroterephthalic acid in wastewater. Baird et al. (1980) combined ion exchange with other adsorption methods and obtained 7090% recoveries of organics from secondary and tertiary effluents. In the precipitation process, specific chemicals or types of substances may be precipitated from aqueous solutions and separated by centrifugation or filtration. For example, humic acids are operationally defined as the basesoluble, acid- and alcohol-insoluble organic fraction in soil or aqueous samples (Martin and Pierce, 1971; Schnitzer and Khan, 1978). Humic materials may be precipitated from aqueous solutions by acidification with glacial acetic acid and the addition of isoamyl alcohol (Martin and Pierce, 1971). This method was applied to freshwater and seawater samples but recoveries were not given. The principal disadvantage of this concentration procedure is lack of specificity. Centrifugation is a useful procedure for separating macromolecular materials, but has limited utility for soluble molecular constituents. Humic substances have been separated by analytical ultracentrifugation by Amburgey (1967). This method has not been developed sufficiently to accommodate large-sample volumes and is currently useful only for analytical purposes. In the gas-stripping process, an inert purge gas sweeps over or sparges through aqueous samples, thereby transporting volatile constituents from

the liquid phase into the gas phase, which permits them to be subsequently trapped cryogenically or on adsorbants. This forms the basis for several analytical procedures, for example, closed-loop stripping (Grob and Grob, 1974; Grob and Ziircher, 1976), the purge-and-trap procedure (Bellar and Lichtenberg, 1974), and head-space analysis (Rook, 1974). Gas stripping is currently limited to analytical-size sample volumes. Combination procedures At times, several concentration procedures are combined to achieve as high a recovery of organics as possible. For large-volume samples, Kopfler and his research group use reverse osmosis in combination with Donnan dialysis, solvent extraction, and adsorption on XAD-2 resin to recover an estimated 35-40% of the organic substances from water samples (Kopfler, 1980a [general]; Kopfler et al., 1977 [reverse osmosis]). This method has been used extensively to prepare samples for biological testing (Tabor et al., 1980 [miscellaneous]; Loper et al., 1978 Imiscellaneousl; Loper, 1980 [general]). Johnston and Verdeven have developed a method that &es silica gel, cation-exchange resin, and anionexchange resin, followed by vacuum distillation. Materials are recovered from the resins by elution with a triethylammonium carbonate buffer and then acetone. Recovery of spiked organic mutagens from river water samples by this parfait/distillation method was found to depend strongly on the stability of the compound in the environmental water (Johnston and Verdeyen, in press [vacuum distillation]). Baird and co-workers have developed a procedure capable of continuously processing large volumes of water. This method uses sequential ion-exchange resin columns and subsequent recovery of the organic material by elution. The resins, in order of use, are Biorad MP-I (macroporous anion-exchange resin), Biorad MP-50 (macroporous cation-exchange resin), XAD-2, and XAD-7 (macroreticular nonionic resins). The resins were extracted with either HzS04, KOH, acetonitrile, or a combination of these. Organic carbon removals from secondary and tertiary effluents were 7U90% (Baird et al., 1980 [ion exchange]; Garrison et al.. 1980 lion exchange]). Carbridenc and Sdika (1979 [miscellaneousl) have develooed an aooaratus to s4LentiaIIy extiact I10bbL

of water with 100 L of chloroform under an inert gas at pH 7,2, and 10, followed by XAD-2 and activatedcarbon adsorption. Total recovery of standards from this system was calculated to be 88 wt %. Extracts of drinking water have been prepared and tested for biological activity. Critical areas Kopfler (1980a) indicated that there are several areas of concern in preparing representative concentrates for biological testing. For example, changes may occur in organic residues between preparation of concentrates and biological testing or chemical analysis. Also, humic materials may bind lower-molecular-weight organic substances; consequently, their recovery is necessary to ensure recovery of the bound constituents. Other potential problem areas are: The sample collection method must permit collection of a representative sample; the sample may require preservation be-

tween sampling and concentration because of concomitant possible artifact production; and the concentration method itself may alter constituents and produce artifacts. Summary of methods Because of the large variety of chemical compounds present either naturally or as industrial contaminants in water samples, no single concentration method available is adequate for concentrating all organics in the water sample. Consequently, in an attempt to concentrate or isolate as much organic matter as possible, most researchers have combined several methods that may become quite complex and technically difficult to achieve. Table I , which summarizes most of the current practical methods for achieving concentration of organics from water samples, indicates the utility of each method along with major advantages and disadvantages.

concentrates lor biological testing

Several of the methods have been used to prepare concentrates for biological testing. Table 2 presents selected examples of these methods along with the principal biological test used and the reference citation. Although the concentration method may be limited with respect to concentrating all organic matter, significant positive results were achieved in most of the studies. There is thus a question as to whether a single concentration method or a combination of methods can be developed to achieve concentration of all organic matter in a water sample, or whether this is necessary. That is, it may be profoundly more simple and economical to use several different concentration methods. This, however, raises the specter of omitting a significantly toxic substance because the concentration methods selected were not adequate for that specific compound.

centrate must be representative of all the organic substances present in the water. Thus efforts must be continued to develop simple but efficient methods of concentrating all the organic materials present; however, this may not be technically possible. It is recommended that methods to evaluate and compare different concentration techniques be developed and applied. This will require increased emphasis on chemical analysis to identify much of the organic material in the concentrates. Measurements of general parameters, such as total organic carbon, cannot be used to reliably compare Concentration techniques.

Recommended methodology Selection of the concentration method must be based on the biological test to be conducted. For example, a long-term feeding study of mice could require organic material from many thousands of liters of water. In addition, the concentration method must be based on the chemical and physical properties of the organic constituents to be tested. Because of technical difficulties in biological testing, highly volatile eonstitwnts have generally been tested as specific chemical compounds rather than as concentrates. Moderately volatile and less-volatile constituents may be tested as concentrates. Concentration of volatile constituents by solvent extraction seems to be the most effective method. For nonvolatile constituents, reverse osmosis in combination with other methods, as used by Kopfler et al. (1977). is apparently the best way to prepare large quantities of organic concentrates. However, if thousands of liters per day must be processed, the method of concentrate preparation must be simpler. Thus, XAD adsorption or activated-carbon adsorption may be preferred. If speeifc classes of compounds or specific chemical compounds are to be biologically tested, the specific concentration method can be tailored to this: for example, the separation of humic materials from water samples by alkaline extraction and acid precipitation.

Kopfler (1980b) proposed that all techniques be compared by determining the recovery of compounds of various solubilities selected to include a range of chemical classes, functional groups, and molecular weights, e.g., selected compounds from the reference compound list prepared by Keith (1979). He recommended the inclusion of aquatic humic substances, b e fore and after reaction with chlorine. Kopfler also recommended standardization of techniques so that contaminants are minimized and remain at constant levels each time the method is used. Contaminants unique to the concentration process must be identified and quantified to determine their effect on and to permit proper evaluation of the biological test. Possible artifacts in the concentration methods must be evaluated, for example, it is suspected that peroxide in ether used to elute adsorption columns may create artifacts. The stability of concentrates during storage must also be evaluated.

Methodology development To estimate the total hazard associated with water, the organic con-

Acknowledgment This research was sponsored jointly hy the U.S. Environmental Protection Agency

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under Interagency Agreements EPAIAG-D7-01027 and DOE-40-593-76 and the Division of Biomedical and Environmental Research, U.S. Department of Energy, under contract W-7405-eng-26 with the Union Carbide Corporation. Before publication, this article was read and commented on by Dr. Lawrence H. Keith, manager, Analytical Chemistry Division. Radian Corporation, Austin, Tex.; Dr. William H. Glaze, head of the Graduate Program in Environmental Sciences at the University of Texas at Dallas (Richardson); and Dr. E. D. Pellizzari, director of the A~lyticalSciences Division of Research Triangle Institute, Research Triangle Park, N.C.

Dr. Robert L. lolley is an enuironmenfal chemisi in the Advanced Technology Secfion, Chemical Technology Division, of the Oak Ridge National Laboratory. His currenf research interests include the analysis of organic constituents in wasfewafer effluents and natural wafers, and chlorination, ozonafion,and UVirradiafion effects on fhese organic corufiluenfs. He is also secrefaryand chairman-elect of the ACS Division of Environmental Chemisfry. References and bibliography General Garrison. A. W. 1977. Ann. N.Y.Acad. Sei., Vol. 298,pp. 2-19. Hits, R. A. 1977. In “Advances in Chromatography”; J. C. Giddings, Ed.; Marcel Dek. ker, Inc.: New York. pp. 69-129. Keith, L.H. 1976. “Identification and Analysis of Organic Pollutants in Water”; Ann Aibor Science Publishers, Inc.: Ann Arbor, Mwh. Keith, L. H. 1979.Emiron. Sci. Techno/.,Vol. 13,No. 12,pp. 1469-1471. Kopfler. F. C. 1980a. “Alternative Strategis and Methods for Concentratin Chemicals from Water“; Presented at the 8econd Symposium on Application of Short-Term Bioassays in the Fractionation and Analysis of Complex Mixtures, Williamsburg, Va. March 4-7. KO fler F C l98Ob “Concentrating Organics r ! f Tbxicity Testing-The Challenge”; Preprints of papers, ACS Div. Environ. Chem.: Vol. 20, No. 1,pp. 103-104. Loper,, J. C. 1980. In “Water Chlorination: Environmental Impact and Health Effecls”: R. L. lolley. W. A. Brungs, and R. B. Cumming. Eds.; Ann Arbor Science Publishers. Inc.: Ann Arbor. Mich., Vol. 3, pp. 937-945. Smith, C. C. 1978. In “Application of ShortTerm Bioassays in Ihe Fractionation and Analysis of Complex Environmental Mixtures”; M. D. Waters, S. Nesnow,J. L. Huisingh, and S. S. Sandhu, Eds.; Plenum Prcss: New York, pp. 229-244. Fnae Concenbation Baker. R. A. 1967. Water Res., Vol. I,

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Baker, R. A. 1967. Water Res., Vol. 1, pp. 97-117. Baker,. R..A. 1969. Water Res., Vol. 3, pp. 717-730. Baker, R. A. 1970. Water Res., Vol. 4, pp. 559-573. Shapiro, J . 1961. Science, Vol. 133, pp. 2063-2064. Mallevialle, J. 1972. Techniques et Sciences Municipales, Vol. 67, No. 11, pp. 1-9.

Lyophilization Aldridge, M. H.; Pressley, T. A.; Chapin, C.; Welebir, A. 1976. “Characterization of Nonvolatile Organic Material During Physical-Chemical Treatment of the District of Columbia Raw Wastewater”; WRRC Report No. 9; Washington Technical Institute: Washington, D.C. Crathorne, B.; Watts, C. D.; Fielding, M. 1979. “The Analysis of Nonvolatile Organic Compounds in Water by High-Performance Liquid Chromatography”; Presented at the Fourth International Symposium on Column Liquid Chromatography, May 7-10, Boston, Mass. Cumming, R . B.; Lewis, L. R.; Jolley, R. L.; Mashni, C. I. 1979. In “Progress in Wastewater Disinfection Technology”; EPA600/9-79-018; A. D. Venosa, Ed., pp. 246252. Dawson, R.; Mopper, K. 1978. Anal. Biochem., Vol. 84, pp. 186-190. Jolley, R. L.; Lee, N. E.; Pitt, W. W.; Denton, M. S.; Thompson, J . E.; Hartmann, S. J.; Mashni, C. I. 1979. In “Progress in Wastewater Disinfection Technology”; EPA600/9-79-018; A. D. Venosa, Ed., pp. 233245. Vacuum distillation Hall, K. J.; Lee, G . F. 1974. WaterRes.,Vol. 8, pp. 239-251. Johnston, J. B.; Ferdeyen, M. K. In press. “Recovery of Mutagens from Water by the Parfait/Distillation Method”; In “Chemistry and Analvsis of Wastewater Intended for Reuse”: W. J: Cooper, Ed.; Ann Arbor Science Pub: lishers, Inc.: Ann Arbor, Mich. Jolley, R. L.; Katz, S.;Mrochek, J. E.; Pitt, W. W.: Rainev. W. T. 1975. CHEMTECH, Vol. 5, pp. 3121318. Katz. S.:Pitt. W. W.: Scott. C. D.: Rosen. A. A. _._ 1972,’Warer Res.,’Vol. 6, pp. 1029-1037. Pitt, W. W.; Jolley, R. L.; Katz, S. 1974. “Automated Analysis of Individual Refractory Organics in Polluted Water”: EPA 660/274-376. Pitt, W. W.; Scott, C. D. 1973. In “Ecology and Analysis of Trace Contaminants”; ORNLNSF-EATC-I; Progress Report, June 1972-January 1973, pp. 309-331. Reverse osmosis Deinzer, M.; Melton, R.; Mitchell, D. 1975. Water Res., Vol. 9, pp. 799-805. Kopfler, F. C.; Coleman, W . E.; Melton, R. G.; Tardiff, R. G.; Lynch, S. C.; Smith, J. K. 1977. Ann. N.Y. Acad. Sci., Vol. 298, pp. 20-30. Kopfler, F. C.; Melton, R. G.; Mullaney, J . L.; Tardiff, R. G. 1975. In “Fate of Pollutants in the Air and Environment”; I. H. Suffet, Ed., J. Wiley-Interscience: New York, Vol. 2, pp. 419-433. Smith, J. K.; Lynch, S. C. 1980. “Concentration of Organics for Toxicity Testing Using Membrane Processes”; Preprints of papers, ACS Environ. Chem. Div.: Vol. 20, No. 1, pp. 105-106. Tardiff, R. G.; Carlson, G. P.; Simmon, V. 1978. In “Water Chlorination: Environmental Impact and Health Effects”; R. L. Jolley, Ed.; Ann Arbor Science Publishers, Inc.: Ann Arbor, Mich., Vol. I , pp. 195-209. Ultrafiltration Macko, C.; Maier, W. J.; Eisenreich, S. J.; Hoffman, M. R. 1979. In “Water-1978”; AIChE Symposium Series 190, Volume 75.

pp. 162-169. McCahill, M . L.; Conroy, L. E.; Maier, W. J. 1980. “Determination of Organically Combined Chlorine in High Molecular Weight Aquatic Organics”; Preprints-of papers, ACS Div. Environ. Chem.: Vol. 20, No. I , pp. 232-233. Milanovich, F. P.; Ireland, R. R.; Wilson, D. W. 1975. Enuiron. Lett., Vol. 8, No. 4, pp. 337-343. Pope, J. Environmental Research Laboratory, EPA, Athens, Georgia. Personal communication. July 23, 1980. Scott, J. 1980. “Membrane and Ultrafiltration Technology”; Noyes Data Corporation: Park Ridge, N.J.

Solvent extraction Bjqrseth, A,; Lunde, G.; Gjfs, N. 1977. Acta Chem. Scan., Vol. B 31, pp. 797-801. Hites, R. A. 1973. J . Chromatogr. Sei., Vol. 11, OD. 570-574. M&re, J. P.; Dietrich, M . W. 1973. J . Chromatogr. Sci., Vol. 11, pp, 559-570. Sheldon, L. S.;Hites, R. A. 1978. Enuiron.Sci. Technol..Vol. 12.No. 10. DD. 1188-1194. Suffet. I. H:: Brenner. L.: Silikr. B. 1976. Enuiron. SCL Technol., Vol. 10, No. 13, pp. 1273-1 275. Yoke, T. L.; Suffet, I. H.; Grochowski, R. J. 1979. In “Measurements of Organic Pollutants in Water and Wastewater”: C. E. Van Hall, Ed.; ASTM STP 686; American Society for Testing and Materials: Philadelphia, Pa., pp. 47-67. Activated carbon Braus, H.; Middleton, F. M.; Walton, G. 1951. Anal. Chem., Vol. 23, No. 8, pp. 11601164. Buelow, R. W.; Carswell, J. K.; Symons, J. M. 1973. J. Am. Water Works Assoc., Vol. 65, pp. 57-73. Dunlap, W. J.; Shew, D. C.; Scalf, M. R.; Cosby, R. L.; Robertson, J . M. 1976. In “Identification and Analysis of Organic Pollutants in Water”; L. H. Keith, Ed.; Ann Arbor Science Publishers, Inc.: Ann Arbor, Mich., pp. 453-477. Fuchs, F.; Kuhn, W. 1975. In “Transactions of Reports on Special Problems of Water Technology, Volume 9-Adsorption”; EPA 600/9-76-030, pp. 182-207. McCabe. L. J.: Svmons. J. M.: Lee. R. D.: RoBeck, G. G . 1970: J. Am. Water Works Assoc., VOI. 62, pp. 670-687. McGuire, M. J . 1980. “Activated Carbon Adsorption of Organics from the Aqueous Phase”; Ann Arbor Science Publishers, Inc.: Ann Arbor, Mich., Vol. 2. Middleton, F. M.; Lichtenberg, J. J. 1960. Ind. Eng. Chem., Vol. 52, No. 6, pp. 99A-102A. Middleton, F. M.; Petit, H. H.; Rosen, A. A. 1962. In “Proceedings of the Seventeenth Industrial Waste Conference”; Purdue University: Engr. Ext. Ser. 112; pp. 454-460. Modell, M.; deFilippi, R. P.; Krukonis, V. 1980. In “Activated Carbon Adsorption of Organics from the Aqueous Phase”; 1. H. Suffet, Ed.; Ann Arbor Science Publishers, Inc.: Ann Arbor, Mich., Vol. I , pp. 447-462. Robertson, J. M.; Toussaint, C. R.; Jorque, M. A. 1974. “Organic Compounds Entering Ground Water from a Landfill”; EPA660/2-74-077. Rosen, A. A. 1976. I n “Identification and Analysis of Organic Pollutants in Water”; L. H. Keith, Ed.; Ann Arbor Science Publishers, Inc.: Ann Arbor, Mich., pp. 3-14. Sanjivamurthy, V. A. 1978. Water Res., Vol. 12, pp. 31-33. ‘Standard Methods for the Examination of Water and Wastewater”; 1976. American Public Health Association, American Water Works Association, and the Water Pollution Control Federation) pp. 535-543, 14th ed. Suffet, I . H. 1980. “Activated Carbon Adsorption of Organics from the Aqueous Phase”;

A n n Arbor Science Publishers, Inc.: Ann Arbor, Mich., Vol. I , Suffet. I . H.; Radizul, J. V.; Cairo, P. R.; Coyle, J . T. 1978. I n “Water Chlorination: Environmental Impact and Health Effects”; R. L. Jolley, D. H. Hamilton, and H. Gorchev, Eds.: Ann Arbor Science Publishers, Inc.: Ann Arbor, Mich., Vol. 2, pp. 561-582. Carbonaceous adsorbents and open-pore polyurethane Denton, M. S.; Dinsmore, S. R.; Brand, J. I.; Beams, J.; Ball, F. L. 1980. Sep. Sci. 7echnol., Vol. 15, No. 3, pp. 587-613. Denton, M. S.; Dinsmore, S. R. 1980. “A Comparison of Synthetic Adsorbents, Including Open-Pore Polyurethane, as Applied to Coal Conversion Process Aqueous Effluent Cleanup”; Presented at the Second Chemical Congress of the North American Continent. Aug. 24-29, 1980, Las Vegas, Nev. XAD resin Aiken, G. R.; Thurman, E. M.; Malcolm, R. L. 1979. Anal. Chem.. Vol. 51. No. 11. DD. .. 1799-1 803. Burnham, A. K.; Calder, G. V.; Fritz, J . S.; Junk, G. A,; Svec, H. J.; Vick, R. 1973. J . Am. Water Works Assoc., Vol. 65, pp. 722-725. Cheh, A. M.; Skochdopole, J.; Heilig, C.; Koski, P. M.; Cole, L. 1980. In “Water Chlorination Environmental Impact and Health Effects”, R. L. Jolley, W. A. Brungs, and R. B. Cumming, Eds.; Ann Arbor Science Publishers, Inc.: Ann Arbor, Mich., Vol. 3, pp. 803-815. Cheh, A. M.; Skochdopole, J.; Koski, P.; Cole, L. 1980. Science, Vol. 207, No. 4, pp. 9092. Dressler, M. 1979. J . Chromatogr., Vol. 165, pp. 167-206. Glatz, B. A.; Chriswell, C. D.; Arguello, M. D.; Svec, H. J.; Fritz, J. S.; Grimm, S. M.; Thomson, M. A. 1978. J . Am. Water Works ASSOC., Vol. 70, pp. 465-468. Grieser, M . D.; Pietrzyk, D. J. 1973. Anal. Chem., Vol. 45, No. 8, pp. 1348-1353. Junk, G. A.; Chriswell, C. D.; Chang, R. C.; Kissinger, L. D.; Richard, J. J.; Fritz, J. S.; Svec, H. J. 1976. Z . Anal. Chem., Vol. 282, pp. 331-337. Junk, G . A,; Richard, J. J.; Grieser, M. D.; Witiak, D.; Witiak, J. L.; Arguello, M. D.; Vick, R.; Svec, H. J.; Fritz, J . S.; Calder, G. V. 1974. J . Chromatogr., Vol. 99, pp. 745762. Kissinger, L. D.; Fritz, J. S . 1976. J Am. Water Works Assoc., Vol. 68, pp. 435-437. Kroeff, E. P.; Pietrzyk, D. J. 1978. Anal. Chem., Vol. 50, NO. 3, pp. 502-51 1. Leach, J. M.; Thakore, A. N. 1975. J. Fish. Res. Board Can., Vol. 32, No. 8, pp. 1249-1257. Malcolm, R. L.; Thurman, E. M.; Aiken, G. R. 1977. In “Trace Substances in Environmental Health-XI”; D. D. Hemphill, Ed.; University of Missouri: Columbia, Mo., pp. 307314. Malcolm, R. L.; Thurman, E. M.; Aiken, G. R. 1980. “Considerations Relevant to the Use of XAD Resins in Concentrating Organics for Toxicitv Studies”: Preorints of Paoers. ACS Enviro&nental Chemktry Divisioi: Vol. 20, NO. 1, pp. 107-108. Pietrzyk, D. J.; Chu, C.-H. 1977. Anal. Chem., VOI. 49, NO. 6, pp. 757-764. Pietrvzk. D. J.: Chu. C.-H. 1977. Anal. Chem.. Vdl. 49, No. 6, pp. 860-867. Pietrzyk, D. J.; Kroeff, E. P.; Rotsch, T. D. 1978. Anal. Chem., Vol. 50, No. 3, pp. 497-502. Rappaport, S. M.; Richard, M. G.; Hollstein, M. C.; Talcott, R. E. 1979. Enuiron. Sci. Technol., Vol. 13, No. 8, pp. 957-961. Renberg, L. 1978. Anal. Chem.,Vol. 50, No. 13, pp. 1836-1838. Thurman, E. M.; Malcolm, R. L.; Aiken, G. R. 1978. Anal. Chem., Vol. 50, No. 6, pp. 775-779. Yamasaki, E.; Ames, €3. N . 1977. Proc. Nut. Acad. Sci. USA, Vol. 74, NO. 8, pp. 35553559. Volume 15, Number 8, August 1981

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Ion exchange Baird, R. B.; Gute, J.; Jacks, C.; Jenkins, R.; Niesess, L.; Scheybeler, B.; Van Sluis, R.; Yanko, W. 1980. In “Water Chlorination: Environmental Impact and Health Effects”; R. L. Jolley, W. A. Brungs, and R. B. Cumming, Eds.; Ann Arbor Science Publishers, Inc.: Ann Arbor, Mich., Vol. 3, pp. 925-9 35. Garrison, W. E.; Nellor, M. H.; Baird, R. B. 1980. In “Wastewater Reuse for Groundwater Recharge,” T. Asano, P. V. Roberts, Eds.; Office of Water Recycling, State of California: pp. 216-254. Junk, G. A,; Richard, J. J . 1980. “Anionic and Neutral Organic Components in Wastewaters by Anion Exchange”; Preprints of Papers, ACS Division of Environmental Chemistry: Vol. 20, NO. 2, pp. 277-279. Scott, C. D. 1971. In “Modern Practice of Liquid Chromatography”; J. J. Kirkland, Ed.; Wiley-Interscience: New York, pp. 287232.

Enuiron. Sci. Technol., Vol. 9, No. 8, pp. 762-765. Dowty, B.; Carlisle, D.; Laseter, J. L.; Storer, J. 1975. Science, Vol. 187, pp. 75-77. Grob, K.; Grob, G. 1974. J . Chromatogr., Vol. 90. DD. 303-313. .Grob,’K.; Zurcher, F. 1976. J . Chromatogr., Vol. 117, pp. 285-294. Novik, J.; Zluticky, J.; Kubelka, V.; Mostecky, J. 1973. J. Chromatogr., Vol. 76, pp, 4550. Pfaender, F. K.; Jonas, R. B.; Stevens, A. A,; Moore, L.; Hass, J. R. 1978. Enuiron. Sci. Technol., Vol. 12, pp. 438-441. Rook, J. J. 1974. Water Treat. Exam., Vol. 23, pp. 234-243. Symons, J . M.; Bellar, T. A.; Carswell, J . K.; DeMarco, J.; Kropp, K. L.; Robeck, G . G.; Seeger, D. R.; Slocum, C. J.; Smith, B. L.; Stevens, A. A. 1975. J . A m . Water Works ASSOC., VOl. 67, pp. 634-647.

Precipitation Martin, D. F.; Pierce, R. H. 1971. Enuiron. Lett., Vol. 1, No. 1, pp. 49-52. Schnitzer, M.; Khan, S . U. 1978. “Soil Organic Matter”; Elsevier Scientific: New York. Centrifugation Amburgey, J. W. 1967. Humic Acid Investigations. K-L-2549, Union Carbide Corporation, Nuclear Division, Oak Ridge, Tenn. Gas stripping Bellar, T. A,; Lichtenberg, J. J. 1974. J . Am. Water Works Assoc., Vol. 66, pp. 739-744. Bellar, T. A.; Lichtenberg, J. J.; Kroner, R. C. 1974. J . Am. Water Works Assoc., Vol. 66, pp. 703-706. Dowty, B. J.; Carlisle, D. R.; Laseter, J. L. 1975.

Miscellaneous Cabridenc, R.; Sdika, A. 1979. In “Proceedings of the European Symposium on Analysis of Organic Micropollutants of Water”; Berlin, Dec. 11-13, 1979. Cumming, R. B.; Lee, N. E.; Lewis, L. R.; Thompson, J. E.; Jolley, R. L. 1980. In “Water Chlorination: Environmental Impact and Health Effects”; R. L. Jolley, W. A. Brungs, and R. B. Cumming, Eds.; Ann Arbor Science Publishers, Inc.: Ann Arbor, Mich., Vol. 2, pp, 881-889. de Greef, E.; Morris, J. C.; van Kri’I C F.; Morra, C. F. H. 1980. In “Water dilohnation: Environmental Impact and Health Effects”; R. L. Jolley, W. A. Brungs, and R. B. Cumming, Eds.; Ann Arbor Science Publishers, Inc.: Ann Arbor, Mich, Vol. 2, pp. 91 3-924. Douglas, G. R.; Nestmann, E. R.; Betts, J. L.;

Mueller, J. C.; Lee, E. G.-H.; Stich, H. F.; San, R. H. C.; Brouzes, R. J. P.; Chmelauskas, A. L.; Paavila, H. D.; Walden, C. C. 1980. Zbid., pp. 865-880. Hemon, D.; Lazar, P.; Cabridenc, R.; Chouroulinkov, 1.; Sdika, A,; Festy, B.; Gerin-Roze, C. 1978. Rev. Epid. et Sante. Pub., Vol. 26, pp. 441-450. Loper, J . C.; Lang, D. R.; Schoeny, R. S . ; Richmond, B. B.; Gallagher, P. M.; Smith, C. C. 1978. J. Toxicol. Environ. Health, Vol. 4, pp. 919-938. Loper J. C.; Lang, D. R.; Smith, C. C. 1978. In “Water Chlorination: Environmental Impact and Health Effects”; R. L. Jolley, D. H. Hamilton. and H. Gorchev. Eds.: Ann Arbor Science Publishers, Inc.: A n n Arbor, Mich., Vol. 2, pp. 433-450. Neal, R. A. 1980. In “Water Chlorination: Environmental lmoact and Health Effects”: R. L. Jolley, W. A.’Brunes, and R. B. Cumming, Eds.; Ann Arbor Science Publishers: Ann Arbor, Mich., Vol. 3, pp. 1007-1017. Payne, J. F.; Martins, I.; Fagan, D.; Rahumtula, A. 1980. In “Water Chlorination: Environmental Impact and Health Effects”; R. L. Jolley, W. A. Brungs, and R. B. Cumming, Eds.; Ann Arbor Science Publishers, Inc.: Ann Arbor, Mich., Vol. 2, pp. 845-850. Tabor, M. W.: Loper, J. C.; Barone, K. 1980. In “Water Chlorination: Environmental Impact and Health Effects”; R. L. Jolley, W. A. Brungs, and R. B. Cumming, Eds.; Ann Arbor Science Publishers, Inc.: Ann Arbor, Mich., Vol. 2, pp. 899-912. Van Rossum, P.; Webb, R. G. 1978. J . Chromatogr., Vol. 150, pp. 381-392. Walton, H . 1980. “Concentration of Nonvolatile Organic Compounds from Wastewater”; Preprints of papers, ACS Division of Environmental Chemistry, Vol. 20, No. 1, pp. 115-117.

POLLUTION CONTROL CHEMIST

A challenaina Dosition for a versatile Pollution Control Wecialist At SOHIO, we have already met dramatic environmental problems. Many had to be solved to complete the Alaska pipeline and other important projects in ou,r dynamic growth. These challenges will certainly continue as we develop energy sources, chemicals and other products through the ’80’s and beyond. Our contlnuing search for constructive answers offers a unique Opportunity for a very special Pollution Control Chemist. As a candidate for this position, you will need a BS and an MS In Chemistry, Biology or Environmental Science. In addition, you must be very familiar with biological waste treatment concepts and analytical procedures and preferably have at least 3 years of recent experlence in wastewater treatment applications. The opportunities of thls position include responsibility for evaluating treatment systems, solving treatment problems and roviding data for conceptual desi ns for new treafnent Systems. As part of a hi f l y skilled group of in-house technical consustants you will:

Conduct field sampling of plant effluents and receiving streams. 0 Coordinate waste load surveys. 0 Provide technical expertise in wastewater.treatment and analysis to engineerin projects. 0 Conduct pilo? studies to develo conceptual desi ns for new wastewater treafnent pjants. You wif need proficiency in problem solving and technical writing and a willin ness to travel nationwide - including Alaska atout 40% of the t,ime. This position also offers exceptional growth otential in many areas of environmental work, o ether with a competitive salary commensurate wigh pur background plus enerous benefits. SOH18 s relocatlon package qualified new hlres Includes a mortgage Interest differential allow. ance, third party home purchase option and other features normally restricted to internal transfers. If this opportunity interests you, please send your resume and pertinent inforrnatlon, in strictesf confidence to: 0

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Environmental Science & Technology

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