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! j ! ltd A 11 tPGHE oo thug y , :Y:; I 'I ttatta i c '' C Water Research Pcrgamon Press 1970. Vol. 4, pp. 265-269. Printed in Great Britain A REVIEW OF CHLORINATED BIPHENYL CONTAMINATION IN NATURAL WATERS Gilman D. Veith and G. Fred Leb Water Chemistry Laboratory University of Wisconsin. Madison, Wis. 53706, U.S.A. (Received 10 November 1969) Abstract--A review of the present state of knowledge concerning environmental contamina tion by organochiorine compounds indicates that the chlorinated biphenyls may be one of the more widespread contaminants. The significance of this contamination has not yet been evaluated due, in part, to the lack of systematic analytical procedures for the quantitative and qualitative determinations of the components of chlorinated biphenyl mixtures. The possibility of the chlorinated biphenyls producing serious errors in chlorinated pesticide analyses is emphasised. - INTRODUCTION Chemical determinations of the types and concentrations of chlorinated pesticides in natural waters have become increasingly important to fish management, wildlife ecology, and water pollution control. Based on gas chromatographic (GLC) analyses of environmental samples, pp'DDE is generally considered to be one of the more widespread contaminants. However, implicit in every GLC analysis is the possibility that unresolved and/or unidentified components which have specific retention volumes similar to that of the desired substance may introduce serious errors in the interpreta tion of the chromatogram. Increasing numbers of investigators have reported the presence of organochiorine compounds in environmental samples which cannot be identified as the common chlorinated pesticides. Although the unidentified compounds have been attributed from presumptive evidence to the metabolites of common pesticides, plasticizers, or chlorinated biphenyls, proper chemical identifications have not been reported. Therefore, when studying natural water systems which receive industrial wastes, it may be more correct to consider unidentified compounds as chlorinated organic contaminants until confirmation techniques are developed. Within the last three years, the chlorinated biphenyls (or polychlorinated biphcnyls- PCB) have received considerable study. The preliminary evidence indicates that this group of organochiorine compounds may be widespread in the environment. For example, Widmark (1967) reported that mass-spectrum analyses of compounds eluting from GLC of fish and bird extracts indicated that unknown organochiorine compounds were present which behaved as chlorinated biphenyls of higher chlorine content. More recently, mass numbers and chlorine numbers per molecule for each peak in Ute chromatograph of commerical chlorinated biphenyl were reported (Jensen et ai, 1968). However, to our knowledge, no spectral data or other confirm atory data for positive structural identification of these compounds have ever been published. . With this improper basis of identification, a number of other publications have followed which identify unknown compounds as chlorinated biphenyls. Since mixtures of chlorinated biphenyls may contain greater than 20 compounds which can only be WATM 4/4--* 265 MOMS 064944 \ t ii I; I !' i t i ti i'.:v t ' 266 Gilman D. Verm end G. Fred Lee resolved by GLC with great difficulty, assignment of unidentified peaks to one of the chlorinated biphenyls has been accomplished by comparison of a chlorinated bipbenyl with the nearest relative retention time. For example, Holden and Maxsden (1967), who had earlier reported the presence of unknown compounds in fish (Holden, 1966), reported the presence of chlorinated biphenyls In seals with no supporting data other than relative retention data from GLC columns. Robinson el al. (1967) reported compounds of unknown identity in marine organisms which gave GLC retention times longer than pp'DDE and microcoulometric response. The authors indicated that the chromatographic characteristics of the unknowns suggested they were not metabolites of the "cyclodiene-type" pesticides as has been proposed by Roburn (1963). Holmes el al. (1967) attributed unknown peaks from GLC to the chlorinated biphenyls and noted that the substances seemed to accumulate in organisms associated with natural waters (seals, fish and birds) to a greater extent than in domestic animals. This work reported relative rentention data with no supporting data. Risebrouoh tl al. (1968 a) and Risebkovoh el al. (1968 b) reported organochlorine compounds in fish, birds and bird eggs which were attributed to the chlorinated biphenyls. With no supporting data and despite the absence ofstructural confirmations for the chlorinated biphenyls, the investigators reported concentrations of the unknowns (as chlorinated biphenyls) as well as ratios of DDT to chlorinated biphenyls. From these ratios, it was concluded that a chlorinated biphenyl fallout pattern existed around industrial centers and that air transport of the contaminants was significant. Koeman el al. (1969) presented GLC chromatograms of extracts from environ mental samples as well as mass numbers and numbers of chlorine atoms per molecule for each peak of the chromatogram. Although no spectral data were presented, the mast number data strongly suggested that chlorinated biphenyls were present. This paper also presented the results of the analytes for each unknown as being "present'' or "absent" in a particular sample, rather than attempting to quantitate the amount of material present THE CHLORINATED BIPHENYLS Since contamination of the environment by chlorinated biphenyls has been impli cated in the brief review presented, the need for the environmental scientist to become familiar with the present state of knowledge concerning these molecules is apparent. Mixtures of chlorinated biphenyls have been manufactured since 1929 and present , registered trademarks for commercial brands include: Arochlor (Monsanto), ' Chlorextol (Allis-Chalmers), Dykanol (Cornell-Dubilier Division, Federal Pacific Electric), Inerteen (Westinghouse), Noflamol (Wagner Electric), Pyramol (G. E.), Therminol (Monsanto) in the U.S.; and Clophen (I. G. Farbenidusttie A. G., Ger many), Fendor (Caffaro, Italy), Kannechlor (Kanegafuchi Chemical Co., Japan), Pyralene (Prodelec, France), and Soval (Russia) (Hubbard, 1964). The chlorinated biphenyls have been used as plasticizers for adhesives, polyvinyl acetates, acrylic resins, in sealing compounds, pipe joint compounds, printing ink, rubber manufactur ing, high pressure-high temperature lubricants, fimgicidal insulations, anti-corrosion, nail coatings, water proofings, diffusion pump fluid, stabilization of polymers, Alb dielectrics, heat preventing coot (Monsanto O/l el al.. 1953). The toxicity a has not been tl indicate that me "safe" is 1.0 mg highly chlorina! with chlorinate reported repeaa biphenyls (Mat effects of Arod cited) to the el $460 to be non More recentl biphenyls to ho tion, and that factor of 1000. dieldrin and D However, in with organoch possibility tha biological core review of the other metabd enzyme indue great at pp'D facts make tot cules have th concentration Some con* studies of off biphenyl. In analyses. Ho have been in make the pec of chemical I For exami step which t* residues (E was treated It was cottd nitration she MQNS 084945 >. t one of the d biphenyl D*N (1967), I dlU other in marine ' licrocouloleriitict of ' pesticides , I hlorinated ' modeled c animals. , lochlorine.... . , ilorinited; Irmeiione " of the ; Jorinated yl fallout aminanta , snvlronmolecule ued, the rat. Thii preeant" V amount .. , .... oo A Review of Chlorinated Biphenyl Contamination in Natural Waters 2(7 dielectric*, heat tranefer media, coax-cable insulations, paints and varnishes, ice preventing coatings, and is an evaporation retardant for pesticide applications (Monsanto O/P1J06; Hubbard, 1964; Hopkins and Hoffman, I9SS; Sullivan it al., 19SS). The toxicity and sublethal effects of the chlorinated biphenyls to biological systems has not been thoroughly evaluated (Reichbl, 1969). Inhalation tests on animals indicate that maximum concentrations of chlorinated biphenyls as vapor which are "safe" is 1.0 mg/m* for the lower chlorinated biphenyls and 0.5 mg/m' for the more highly chlorinated biphenyls (Hubbard, 1964). Continuous or repeated skin contact with chlorinated biphenyl leads to a condition called "chloracnc" which has been reported repeatedly with industrial workers handling products containing chlorinated biphenyls (Meios tt al., 1953). Suluvan and Hornstein (1953) found no toxic effects of Arochlor 5460 on flies, but the chlorinated terphenyls were toxic (no levels cited) to the elm leaf beetle (Duda, 1957). Deonier tt al. (1946) found Arochlor 5460 to be non-toxic at 0.1 ppm (24 hr) to the larvae of Anophtlis tptadrimaculatut. More recently, Lichtenstein tt al. (1969) reported the toxicity of the chlorinated biphenyls to houseflies (Z>, melaimgasttr) decreased with increasing degree ofchlorina tion, and that the chlorinated biphenyls appear to be less toxic than dieldrin by a factor of 1000. The chlorinated biphenyls were found to increase the toxic effect of dieldrin and DDT on houseflies. However, in addition to investigating the sources of environmental contamination with organochlorine compounds, the environmental scientist is concerned with the possibility that these organochlorine molecules may exhibit detrimental effects on biological communities at sublethal levels. Kupfer (1967) has presented an extensive review of the effects of chlorinated pesticides on steroid hydroxylase induction and other metabolic systems. Also, Risebrouoh it al. (1968 b) have demonstrated that enzyme induction by the chlorinated biphenyls (Arochlor 1262) was five times as great as pp'DDE or technical DDT as determined via ocstradiol degradation. These facts make tolerance limits set by bioassay less significant since organochlorine mole cules have the capacity to produce physiological effects in organisms at sublethal concentrations. ' In impli- ' present tsanto), ' ' Pacific 0. &), U Oerlaitah), rinated aerylie Ihcturrosion, /. '' .. nyere. .. ' ANALYTICAL PROCEDURES Some controversy has been generated over the analytical procedures utilized in studies of organochlorine contaminants which have been attributed to the chlorinated biphenyl. In general, the procedures are similar to typical chlorinated pesticide analyses. However, chemical reactions such as dehydrohalogenation and nitration have been introduced prior to electron capture gas chromatography in attempts to make the procedures more selective for the chlorinated biphenyls. It is the addition of chemical treatment steps which has caused disagreement in the literature. For example, alter extract dean up, Jensen and Widmark (1967) used a nitration step which is similar to that used in removing DDT and metabolites from toxaphene residues (Ebro tt al., 1967; Kawano tt al., 1969). Briefly, the concentrated extract was treated with a mixture of HjSO* and HNOj (cone. 1:1, v/v) at 0C for 5 min. It was concluded incorrectly that only PCB and BHC isomers are unaffected by the nitration step. Risebrouoh tt al. (1969) have reported the use of similar procedures. V: MGNS 084946 u J I' t r I: !. I' 4 j .] ' "' \ ' oo . 261 Gilman D. Verm and O. Fred Lib To the contrary, Reynolds (1969) has been unable to repeat the nitration itep reproducibiy for a number of reasons. First, the reaction is not specific for the PCB and BHC isomers, since heptachlor epoxide remains unaffected by nitration. Also, the work of Bevenue (Erro, 1967; Kawano, 1969) hBs demonstrated that toxaphene, the reaction product of the chlorination of camphene which produces in excess of 20 unresolved peaks on GLC, is apparently unaltered by nitration. Second, Reynolds found some loss of the earlier eluting chlorinated biphenyls during nitration. Third, and most significant, peaks with longer retention volumes appeared in the chromato grams after nitration. These peaks resulted from the nitration of other aromatic mole cules in the mixture because nitro groups reduce the vapor pressures in the gas phase (GLC) and the aromatic nitro grouping has a high affinity for the secondary electrons in the electron capture detector. Results of studies of this laboratory (Vbith and Lee, 1969) have substantiated earlier reports (Degursb, 1969) that fish and natural waters in several areas of Wisconsin contain unidentified organochlorine contaminants. Using essentially the same pro cedures discussed by Reynolds (1969), the resulting chromatograms contain many peaks which have retention volumes similar to those of components of several com mercial chlorinated biphenyl mixtures. However, components with corresponding retention volumes were also observed in chromatograms of technical chlordane, heptachlor epoxide, benzene hexachloride, and toxaphene, as well as analytical standards of a number of the DDT family of pesticides. Accordingly, qualitative and quantitative interpretations of such chromatograms from Wisconsin fish and water await more detailed and systematic investigations of the extracts. CONCLUSIONS The preliminary evidence of the past several years, which has been reviewed in this communication, indicates that the environment associated with natural waters is becoming contaminated with unidentified organochlorine compounds from unknown sources. The facts that chlorinated biphenyls have been strongly implicated as con taminants, that the chlorinated biphenyls have been widely used in industry and have been prepared commercially since 1929, and that the mixtures produce GLC peaks with retention volumes similar to common chlorinated pesticides create a need for basic studies concerning analytical procedures for chlorinated hydrocarbons. Also, it is apparent that comprehensive and systematic investigations into the chemistry and the physiological effects of the contaminants as well as the degree and sources of the contamination are essential before control measures can be considered. REFERENCES ^ Daovarn P. 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