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POLYCHLORINATED BIPHENYLS CRITERIA: - INTROOUCTIC'iV: Aquatic Life - 0.001 ug/1 in freshwater; 0,01 ug/1 in marine water * . r * p vs 0 YIm-u. Polychlorinated.biphenyls (PCB'.s) are a class of compounds produced by the chlorination of biphenyls and are known commercially as Aroclors^. The-degree of chlorination determines their chemical properties and generally their com position can be identified by the numerical nomenclature, e.g. Aroclor 1042, Aroclor 1054, etc. The first two digits represent the molecular type and the last two digits the average weight percent of chlorite (NTIS, 1972). ' Identification of PCB's in the presence of organochlorine pesticides such as DDT and DDE has been extreemely difficult in the past because of their similar chromatographic characteristics (P.isebrcugh st al., 1968). In PCD analysis today, however, the interference of organochlorine hydrocarbons is overcome by sequential column chromatography on Florsil and silica gel {Armour and Burke, 1970; F2A, 1971)., Gas-liquid chromatography with highly sensitive and selective detectors has been e^-p Toyed successfully in the sub-micron range (tiebecker and Puglisi, 1971). '. ' PC3 compounds ere only slightly soluble in water; highly soluble in fats, .oils and nonpolar liquids, and highly resistant to both heat and biological degradation (NTIC, 1972). Typically, the specific gravity, boiling point, and melting point of PCB's increase with chlorine content as exemplified in the following table of valorization rates. HONS 205487 % Chlorine 21 32 42 48 54 . 60 ' 62 Vaporization Rats at 100 C (q/cn^/hr .00174 .00084 .000338 .000152 .000053 ^ .000013 .000009 PCB's are relatively non-flaramable, have superior cooling, insulating, and dielectric properties and principally are used in the electrical industry. In 1970, the sale of PCB-containing products as additives to'paints, plasti cizers, pesticides and the encapsulating of carbonless carbon paper was dis continued by the producer. The sale of PCB compounds for heat transfer fluids was discontinued in 1971. Accordingly, the only remaining use of PCB compounds is for capacitors and transformers (NTIS, 1972). - - As a-consequence of past wide usage of PCB's over a long period, they are ubiquitous and have been found to have adverse environmental effects. Even a total cessation of the manufacture and use In PCB's would not be expected to result in disappearance of the material, and extinction from the environment is expected to take many years. Exposure to PCB is known to cause skin lesions {Schwartz and Peck, 1543} and to increase, liver enzyme activity that may have a secondary effect on reproductive processes p.issbrcugh, I98i Street et ci., 19o3; Visserran et si., 1370). it is - II yupVWB'M ............. p HONS 205488 not clear whether the effects are due to the PCB's or their contaminants, the chlorinated dibenzofurans, that are highly toxic (Bauer et al., 1961; Schulz, I960; Varrett, 1970). While chlorinated dibenzofurans are a by-product of PCB production. It is not known whether they are also produced by the degrada tion of PCB's (NAS, 1974). ____ / : An epidemiological study on severe poisoning by rice oil contaminated with PCB's in 1967 indicated that about'0.5 grams Ingested over a period of ap- \ proximately one month was sufficient to cause "Yusho" disease. Many of those affected showed no signs of relief after about three years (Kuratsume et al., 1969). It Is estimated on the basis of 194 samples that 4l\ to 45 percent of the general United States population may have PCB levels of T.O mg/kg or higher (net weight) in adipose tissue (Price and Welch, 1972). It appears, therefore, t that PCB may accumulate in the human body. On this basisj it can be calculated that a daily intake of O.C2 mg would require-about 70 years to be toxic. \ Applying a safety factor of 10 would[^permit a daily intake of 0.002 mg, and assuming a two-liter per cay intake, suggests a permtssaible concentration in water tov.be 0.001 mg/l (KAS, IS74). ct As a consequence of widespread pollution, appreciable PC3 residues exist in fish. Analyses of 40 fish from the 1970 National Pesticide Monitoring Program indicated only one to contain less than 1 ug/g PCB with the ten highest residue levels ranging frcm 19 ug/g to 213 ug/g whole body weight (NAS, 1974). Studies of "the Milwaukee Piver revealed ambient water concentrations of 2.0 to 2.8 ug/1 and residue levels in fish as high as 405 ug/g (Veith and Lee, 1971). ** Cpsr* L1V9 -r. Isvsls hsvfi tssn rsp-rtsd to tc HONS 205489 ~0.0l ug/1 with mean residue levels in large coho salmon of about 15 ug/gKJ ^'r (Veith, 1973). By contrast, residues in ocean fish generally have been below 1 ug/g (NAS, 1974). Based on Lake Michigan data, which indicate that at a level of 0.01 ug/1, the fish tissue concentration exceeds a level found to be non-hazardous to man, a criterion of 0.00.1. ug/1 in freshwater appears warranted. -------. . ----------------- ------- ------------- ----- - ---- -T------------------ ----- Polychlorinated Biphenyls have been found to be toxic to aquatic organisms i end to exhibit a wide variation in toxicity,as a function of the organism and k* the chlorine content of the PCB. Midge reproduction was reduced at 0.45 ug/1 of Aroclor 1254 and reproduction of Daphnia magna was reduced at 1.3 ug/1 (Nebeker and Puglisi, 1974). The highest concentration of Aroclor 1248 having no .chronic effect on the fathead minnow was about 0.3 ug/1 (Brungs, 1974). Observed PCB bio-concentrations in aquatic organisms range over six orders of magnitude. Bluegills exposed to Aroclors 1248 and 1254, exhibited a bioac cumulation factor of 7.1 x 10^ (Stalling and Mayer, 1972). The bioaccumulation factor for gizzard shad in the Saginaw River (Michigan) varied between . 0.6 x 105 and 1.5 x IQ5 for Aroclor 1254 (Michigan Wizer Res. Comm., 1973). Fathead minnows in water containing 0.3 ug/1 of ArotTcr 1245 concentrated it ' ,3 X 10 times (Brungs, 1974). Applying lake Michigan; coho salmon residue data to Lake Michigan ambient water data taken at the sans time and location suggests a bioaccumulation factor of 1.5 x 10. The Food and Orug Administration guideline for protecting the health of human consumers'of fish is 5 ug/g In tissue residue af the fish. A residue level of 2'ug/g in fish consumed by commercial ranch mink has been shown to prevent survival of offspring (Ringer et al., 1972). Reproduction was almost totally eliminated in ranch nink fed a beef diet containing ug/g of HONS 205490 I ''Aroclor 1254 (Platonov/ and Kalstad, 1973). This suggests that a mink-food tissue level of not more than 0.5 ug/g would be required to protect the wild life consumer. Surveys of Escambia Bay (Florida) during the period September 1969 to pecember 1971 have produced data on the pathways and effects of PCB's in the estuarine and marine environments. Through the major PCB source, accidental leakage from a PCB manufacturing plant has been terminated, residues continue to appear in aquatic organisms of the bay (Duke, 1974). The sediment reservoir of Aroclor 1254 is* thought to be a continuing source of this PCB to biota of Escambia Bay. After periodic sampling and analysis of both filtered and unfiltered water from homogeneous surface to bottom water columns, little recoverable Aroclor 1254 was found in the filtered samples. These observations suggest that most of the chemical was attached to sus^nded particles. The initial survey of Escambia Bay blcta revealed fish, shrimp, and crabs with levels as high as 12 ug/g. Higher levels were detected in higher trophic levels than shrimp, wnicn could implicate a chain transfer from -sediment to large animals. Median PCB concentrations in whole fish of eight species from Long Island Sound oooained in 1970 were resorted to be In the order of 1 ug/g, as were ccmparaole concentrations off the coast of Southern California.(Hays and Risebrouch, 1972; Rlsebrough, 1969). /* Few d$,ta existed prior to 1959-1971 on the effects of PCB's on marine 'organisms. From the Escambia Bay data, which include flow-through bioassays ' with residue analyses where possible, the following conclusions were reached: (1) all of the Aroclors tested are acutely toxic for certain estuarine organism; IM--M mm MONS 205491 (2) bioassays lasting longer than 96 hours demonstrated that acute toxicity tests underestimate toxicities of some Aroclors and that Aroclor 1254 is toxic to commercial shrimp at less than 1 ug/1; (3) fish, particularly sheephead minnows, are extremely sensitive to Aroclor 1254 with 0.1 ug/1 being lethal to fry; and, (4) acute toxicity of Aroclor 1016 to estuarine organisms is sinp'lar to the toxicity of other Aroclors^but appears less toxic to fish in long-term exposures than does Aroclor 1254 (Duke, 1974). , * ` Oysters were sensitive to Aroclor 1260 with growth diminished by 44 percent In 10 ug/1 and by 52 percent in 100 ug/1. Approximately 10 percent of the pink shrimp died in 100 ug/1, but no apparent effects on pinfish were noted at 100 ug/1. Aroclor 1254 had no apparent effect on juvenile pinfish at 100 ug/1 in . 48-hour flow-through tests, but killed 100 percent of the pink shrimp. At 100 ug/1 Of Aroclor 1254 for 96 hours, shell growth was inhibited but decreased only 41. percent at levels of 10 ug/1. - The toxicity of Aroclor 1248 and 1242 to shrimp and pinfish was similar to that.of Aroclor 1254. Aroclor 1242 was toxic to oysters at 1D0 ug/1. Killfish exposed to 25 mg/1 of Aroclor 1221 suffered an S5 percent mortality. . In 96-hour bioassays, Aroclor 1016 was toxic to an estimated 50 percent of the oysters, brown shrimp, and grass shrimp at 10 U3/I; it was toxic to 18 percent of the pinfish at 100 ug/1. -' Young oysters exposed to Aroclor 1254 in flowing sea water for 24 weeks experienced reduction in growth rates at 4.0 ug/1, but apparently were not -affected by. 1.0 ug/1. Oysters accumulated as /*much as 101,000 t'imes the test water concentration of 1.0 ug/1. General tissue alta^eticis ip the vesicuU*' MONS 205492 -7- around the diverticula of the hepatopancreas were noted in the oysters exposed to 5.0 ug/1. Ho significant mortality was observed in oysters exposed continu ously to 0.01_uq/l of Aroclor 1254 for 56 weeks (Duke, 1974). Blue crabs apparently were not affected by 20 days' exposure to 4.0 ug/1 of Aroclor 1254. Pink shrimp exposed under similar conditions experienced a 72 percent mortality. In subsequent flow-through bioassays, 51 percent of the juvenile shrimp were killed by Aroclor 1254 in 15 days and 50ppercent of the adult shrimp vfere --illed at 3.0 ug/1 in 35 days. From pathological examinations of the exposed pink shrimp, It appears that Aroclor 1254 facilitates or enhances the expression of latent viral infections. " Aroclor 1254 was lethal to grass shrimp at 4.0 ug/1 in 16 days, to amphipods at 10 ug/1 in 30 days, and to juvenile spot at 5.0 ug/1 after 20 to 45 days. Sheephead minnows were the most sensitive estuarine organisms to Aroclor 1254 with 0.3 ug/1 being lethal to the fry within 2 weeks. Aroclcr 1015 in two different 42-fay flow-through bioassays caused signi ficant mortalities of pinfisii at 32 ug/1 and 21 ug/1. Pathological examination of those exposed to 32 ug/1 revealed several liver and pancreatic alterations. . Sheephead minnows in 25-day .Aroclor 1015 flow-through bioassays were not affected by concentrations of 10 ug/1 or less, tut died at 32 and 100 ug/1. The bioaccumulation factors for the different flow-through bioassays are surnsarized below; m mi wtVM MONS 205493 Aroclor 1254 ' 1254 1254 1254 1254 1016 1016 Organism Oyster Blue Crab Grass Shrimp " Spot Pinfish ' Pinfish Sheephead Minnow Time 30 days 20 days 7 days 1 -28 days . 35 days *'42 days Accumulation Facts (as a multiplier of tes water concentrations) 1.01 x 105 4 x 103 3.$x 103 to 11 x 103 37 x 103 21.8 x 103 11 x 103 to 24 x 103 2.5 x 103 to 8.1 x 103 Evidence is accumulating that RGB's do not contribute to shell thinning of bird eggs (NAS, 1974). Dietary PCB produced no shell thinning in eggs of Mallard ducks (Heath et al., 1972). PCB's may Increase susceptibility to infectous agents such as viral diseases (Friend and Trainer, 1970), and increase the activity of liver enzymes that degrade steroids, including sex hormones (Risebrough et al., 1953; Street et al., 1968). Laboratory studies have indi cated that PCS with ics derivatives or metabolites, causes embryonic death of birds (Voss and Kosman, 1970), C1 MONS 205494 -y- REFERENCES CITED ~ Armour, J.A., and O.A. Burke, 1970. Method for separating polychlorinated biphenyls from DDT and Its analogs. Assoc. Offic, Analy. Chem. 53:761. Bauer, H.,*K.H. Schultz, et al_., 196*1. Occupational poisonings 4n the production of chlorophenol compounds. Arch Gewerbepath 18:538. Brungs, W.A., 1974. Testimony In the matter of proposed toxic pollutant effluent standards for Aldrin-Dleldrln et sH. FWPCA (307) Docket #1. ' FDAa 1971. U.S, Dept, of H.E.W. Pesticide Analytical Manual,-Vol. I and II. ' Friend, H., and D.O. 'Trainer, 1970. Polychlorinated biphenyl interaction with duck hepatitis virus. Science, 170:1314. . Hays, H. and R.W. Risebrough, 1972. Pollutant concentrations in abnorman "'ring tern from Long Island Sould. A"K 89:19. Heath, R.G., J.W. Soann, et al_., 1972. Effects of polychlorinated biphenyls on birds. Proceedings IV International Ornithological Congress (In Press). Kuratsuna-; Mr, Y. "orckawa, e al_., 1953. An epidemiologic study on "Yusho" or chlcrobipheryls poisoning. Fukucaka Acta Med. 60:513. Michigan Water r.es. Coion., 1973. Monitoring for polychlorinated biphenyls in the aquatic environment. National Academy of Sciences, 1974. Water quality criteria, 1972. ` Nebeker, A;V., and F.A. Publlsl, 1971. PC3 Newsletter, p. 19. - Nebeker, A.V., and F.A. Publisi, 1974. Effect of polychlorinated biphenyls MONS 205495 -l (PCB's) on survival and reproduction of Dapnnia Gammarjs and Tanytorsus. Trans. Amer. Fish. Soc. (In press). National Technical Information Service, 1972. Polychlorinated biphenyls and the environment. HTIS Interdepartmental Task Force, Washington, D.C. Platonow, N.S., and L.H. Kalstad, 1973, Dietary effects of polychlorinated biphenyls on mink. Can. Jour. Comp. Med/ 37:391. - Price, H.A., and R.L. Welch, 1972. Occurrence of polychlorinated biphenyls in humans. Environmental Health Perspectives (In Press). Ringer, R.K., R.J. Aulerich, ert al_., 1972. Effect of dietary polychlorinated biphenyls on growth and reproduction of mink. Amer. Chem. Soc. National Meeting Reprints of Papers. 12:149. . Risebrough, R.W., 1969. Chlorinated hydrocarbons In narlne ecosystems. In: Chemical Fallout, M.W. Miller and G.G. ^erg, eds., (C.C. Thomas, Springfield, pp. 5-23. . Risebrough, R.W., R.J. Huggett, et aK, 1968. Pesticides: transatlantic movements In northeast trades; Science, 159:1233. Risebrough, R.W., P.Rieche, et al., 1952. Polychlorinated biphenyls in the global ecosystem. Nature, 220:1098. $chul2, K.H, 1568. Clinical picture and etiology of chloracne. Arbeitsmaa. Sozialmed. Arbeitshgy 3:25. Reprinted In translation in U.S., Congress. Senate, Committee on Commerce, Effects of 2, 4, 5-T on man and the environment: Hearings, 91st Cong., 2nd sess., pp. 336-341. MQNS 205496 -11- ' Schwartz, l. and S.M. Peck, 1943. Occupational acne. New York State Med. 43:1711. Stalling, D.L., and F.L. Mayer, Jr., 1972. Toxicities of PCB's to fish and environmental residues. Environmental Health Perspectives, 1:54. Street, J.C., F.M. Urry, et-al., 1958. Comparative effects of polychlorinated biphenyls and organochlorine pesticides in induction of hepatic microsomal enzymes. Amer. Chem. Soc., 158th National Meeting, Sept. 8-12, 1968. .\ \ Varrett, J., 1970. Statement in U.S. Congress, Senate, Conmittee on Commerce, Effects of 2, 4, 5-T on man and the environment: Hearings, 91st Cong., 2nd sess., pp. 190-360. Veith, G.D., 1973. Chlorinated hydrocarbons in fish from lake fish. Final report, EPA Grant 1602 PBE. Veith, G.D., and G.F. Lee, 1971. Chloroblphenyls (PCB's) in the Milwaukee River. Water Res. 5:1107. Yoss, J.G., and O.H. Koe.car,, 1970. Comparative toxicologic study with poly chlorinated biphenyls in chickens with special reference to porphyria, edena, formation, liver nebrcsis, and tissue residues. Toxicol. Appl. Pharmacol. 17:655* - Wassermert, M., D. 'rTasserr.ir, et al., 1=70. The effect of organochlorine insecticides-on serum colesterol level in people occupationally exposed. Bull. Environ. Cont3m. Toxical.' 5:368. K"l<Sr Vcn-;,^ "? MONS 205497