Document vVe3Kxm5xRyb2R79JNd0ypr9Z

( of the l(CITCE). oud: dpt, Inglmd tOCKHIS Ivtnii, USA Hof Swlutrltnd KYssnatfiGHe USA tNS! (ng papers on eh year, idea Ada fhin uttha rapidly ImleeAeta; MM electrodes snt valencyit,tee ctrodasln lion copy 11/M WWw kwjtmxiNcgefivpbyrslliSTO. VoTe, pp. HS-itt. Milled In Oku Brltsta .. ; A REVIEW OF CHLORINATED BIPHENYL r Vi CONTAMINATION IN NATURAL WATERS ; >! Oilman D. Veith and 0. Fxeo La Water Chtmtury Ubor*iory ~ Ualvmliy of Wisconsin, Madison, Wit. 706, U.3.A. ' .. . __ ' (Atetfatd 10 Noctmber IK9) ___ Afrstrocf--A review of the present Mate of knowtodfe oooeemtns environmental contamlMlion by ortanoehleHne eompeundi indicate* that the chlorinated biphenyl* may be one of tha more widespread contaminants. The slfniflcanee of this contamination has not yel basn evaluated due, la part, to tha taefc of systematic analytical procedures for the quantitative and qualitative determinations ofthe components ofchlorinated biphenyl miaturee. The possibility of tha chlorinated biphenyls producini serious errors In chlorinated pesticide analyses Is emphasised. . ... _____,_____ ___________ . . _____ ........... ... INTRODUCTION Chemical dctcrmlMtiom of the types Md concentration! of chlorinated ptitiddet In netural wnlcre have become increasingly important to fUh management, wildlife ecology, and water pollution control. Bated on gw chromatographic (OLC) analytes of envlronmenul samples, pp'DDB b generally conildertd to be one of the man wideepraid contain!nantt. However, implicit in every OLC analyeli b tha powibility that unreeolved and/or unidentifted componenb which have specific retantlon volumes Mar to that of tha deiirad substance may Introduce aarioue arrora in the Interpreta tion of the chromatogram. Increasing numberi of invaetigaton have reported the pretence of organochlorine compound! In environmental simples which cannot bo identified at tha common chlorinated pesticides. Although the unidentified compound! have been attributed bom presumptive evidence to the metaboiltM of common pesticides, plastidiera, 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 m chlorinated organic contaminants until confirmation technique! are developed. Within the hut three years, the chlorinated Mphenyb (or polychlorinated biphenyls- PCB) have received considerable study. The prellmlnaiy evidence indicates that tbit group of organocMorino compounds may be widespread in die environment. For example, Widmamc (1947) reported that raatt-spectrum analytes of compounds luting bom OLC of fish and bird extracts indicated that unknown organodiiorint oompounds wen present which behaved as chlorinated biphenyls of higher chlorine content. Mon recently, mass numbers and chlorine numbers per molecule for such peek its tha chromatograph of eommerical chlorinated biphenyl wen reported (hracN ii a/., I96<). However, to our knowledge, no spectral data or other confirm atory data for positive structural Identification of. these oompounds have ever been published. -' With this Improper basis of identification, t number of other publication! have followed which Identify unknown compounds at chlorinated biphenyls. Since mixtures of chlorinated biphenyls may contain greater than 20 oompounds which can only ha warn S/e-e . . .. MS 0a^70 266 Oilman D. Vtmi and O. Fato 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 biphenyl with the nearest relative retention time. For example, Hoidf.n and Marsdcn (1967), who had earlier reported the presence of unknown compounds in fuh (Holoun, 1966), reported (he presence of chlorinated biphenyls in seals withjio supporting data other than relative retention data from GLC columns. * Rodinson et at. (1967) reported compounds of unknown identity in marine organisms which gave GLC retention times longer than pp'DDE and microcoulo- toetric response. The authors indicated that the chromatographic characteristics of the unknowns suggested they were not metabolites of the "cyclodienc-type" pesticides as has been proposed by Rodurn (1965). Holmes et et, (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. RrsPBROUOH et at. (1968 a) and Risebrouoh et at. (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 (es chlorinated biphenyls) as well as ratios of DDT to chlorinated biphenyls. From these ratios, it was coocludcd that a chlorinated biphenyl fallout pattern existed around Industrial centers and that air transport of the contaminants was significant. Kocman et at. (1969) presented GLC chromatograms of extracts from environ-, mental temples as well as mass numbers and numbers of chlorioe atoms per molecule for each peak of the chromatogram. Although no spectral data were presented, the mats number data strongly suggested that chlorinated biphenyla were present. This paper alio presented the results of the analyses 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 briefreview presented, the need for the environmental scientist to become familiar with the present stale 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 (Allit-Chalmen), Dykanol (Cornell-Dubilier Division, Federal Pacific Electric), Jncrteen (Westinghouse), Noflamol (Wagner Electric), Pyramot (G. E.), Thtrminol (Monsanto) in the U.S.; and Clophen (I. O, Farbenidustrie A. G., Ger many), Fenclor (Caffaro, Italy), Kannechlor (Kancgnfuchi Chemical Co., Japan), Pyrolene (Prodelee, France), and Soval (Russia) (Hubbard, 1964). The chlorinated biphenyla have been used as plasticisers for adhesives, polyvinyl acetates, acrylic resins, in sealing oompounds, pipejoint compounds, printing ink, rubber manufactur ing, high pressure-high temperature lubricants, Aingicida! insulations, anti-corrosion, nail coatings, water proofings, diffusion pump fluid, stabilization of polymers, dielectric', preventing (Mossasio et e/., 1955) The toxic has not Ih indicate tha "safe" is I t highly chlo; with chlorr reported ref biphenyls ( effects of A cited) to ll 5460 to be More ret biphenyls t* lion, and t factor of l dieldrin an- However with organ possibility biological t review of t other met* enzyme in* great as pp facts make cules have eoncentrat Some ei studies of' biphenyl, analyses. I have been make the ofchemicr For ea step whief residues (I was treat* It was cor nitration > HONS 083171 f te of the biphenyl < (1967), 4,196b). tt oilier marine e >uloittict of .sticidct rlneicd oeiaicd nimali. hlorine rinated lalioni of the mated fkllout ilnanu vironlecufe d. ike . Thii mm'' nounl impll.come arent, tsent .ate), icifie E.), Cer.an), ated 7llc lurlon, err, A Review of Chlorinelcd Diplienyl Contemlnalion In Natural Walen 267 dieleclrict, heat transfer media, coax-ctblc insulaiions, paints and varnishes, ice preventing coalings, and it an evaporation retardant for pesticide applications (Monsanto O/l'L-306; Hurraed, 1964; Hopkins and Hopfsian, 1953; Suluvan era/., 1955). The tonicity and tuhlcthal elTecls of (he chlorinated biphenyls to biological systems has not been thoroughly evaluated (Rficiicl, 1969). Inhalation tests on animals indicate that maximum concentrations of chlorinated biphenyls as vapor which are ''safe" it 1.0 mg/m* for the lower chlorinated biphenyls and 0.5 mg/m' for the more highly chlorinated biphenyls (Huosard, 1964). Continuous or repeated skin contact with chlorinated biphenyl leads to a condition called "chloracne" which has been reported repeatedly with industrial workers handling products containing chlorinated biphenyls (Matos el at., 1953). Suluvan and Hornstein (1953) round 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 er at. (1946) found Arochlor 5460 to be non-toxic at 0.1 ppm (24 hr) to the larvae of Anephclet fuadrimeculena. More recently, Lichtenstein cr of. (1969) reported the toxicity of the chlorinated biphenyls to houseflies (D, melanogaiitr) 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. Kupfur (1967) has presented an extensive review of the effects of chlorinated pesticides on steroid hydroxylase induction and other metabolic systems. Also, Rurouoii cl al. (1961 b) have demonstrated that eniyme Induction by the chlorinated biphenyls (Arochlor 1262) was five tinea as great at pp'DDE or technical DDT as determined via oestradiol degradation. These facts make tolerance limits act by Moatsay less significant since organochlorine mole cules have the capacity to produce physiological effects in organisms at sublethal concentrations. ANALYTICAL PROCEDURES Some controversy has been generated over the analytical procedures utilised 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 ofchemical treatment steps which hat caused disagreement in the literature. For example, after extract clean up, Jensen and Widsiark (1967) used a nitration step which it similar to that used in removing DDT and metabolites from toxaphene residues (Brro er f., 1967; Kawano cl el., 1969). Briefly, the concentrated extract was treated with a mixture of H,S04 and UNO, (cone. I. I, v/v) at 0*C for S min. It was concluded Incorrectly that only PCB and BHC isomers are unaffected by the nitration step. Risesrouok er el. (1969) have reported the use of similar procedures. MGNS 083272 Ml Oilman D. Vam and G. Fxio Lit To the contrary, Reynolds (1969) has been unable lo repeat the nitration step rcproducibly for a number of reasons. First, the reaction is not specific for the PCB and BHC isomers, since hcplachlor epoxide remains unaffected by nitration. Also, the work of Revenue (Eaao, 1967; Kawano, 1969) has demonstrated that toxaphene, the reaction product of the chlorination of camphene which produces In excess of 20 unresolved peaks on OLC, 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 ofother aromatic mole cules in the mixture because nitro groups reduce the vapor pressures in the gas phase (OLQ and the aromatic nitro grouping has a high affinity for the secondary electrons in the electron capture detector. Results of studies ofthis laboratory (Vcith and Lai, 1969) have substantiated earlier reports (Dbouxsc, 1969) that fish and natural waters in several areas of Wisconsin contain unidentified organoehloriae 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, benaene hexachlorlde, and texaphene, at 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 eyttemalic 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 la becoming contaminated with unidentified organochlorine compounds (Torn 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 OLC peaks with retention volumes similar to common chlorinated pesticides create a need for basic studies concerning analytical procedures for chlorinated hydrocarbons, Alto, it it apparent that comprehensive and systematic Investigations into the chemistry and the physiological effects of the contaminants as well aa the degree and sources of the contamination are essential before control measures can be considered. 2Houu". iii. i: HOLM(.,lr. Nni'ii T RR3'" HUBKARP I Chtru )MMS S. Dffi Jink* % Kawan*^ (tilt* Ckm iCOtMAS# ftbh, r 111. t icumc* n bolt* iJCNTtNi: ber*< MlKaJ.1.JM. \ Moniant fUlCHCl. . Wild1 RlYNOpaiR!) UtMBftUb law lUtt<*' cMof RmiMb pohe ROMNK? dtkK i Roaww Suuiv* dies SumO*W*** I VwmC n*r Wbmam ' REFERENCES DtotiMi P. 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