Document bB9wq8K2YwkZ5LMXz2bxNNd06

Gas Chromatographic Characteristics of Authentic Chlorinated Dibenzofurans- Identification of Two Isomers in American and Japanese ' Polychlorinated Biphenyls Retention times of 15 authentic standards of chlo rinated dibenzofurans containing from three to six chlorine atoms were determined relative to dieldrin on gee chromatograph columns of four differ ent polarities (3% OV-1; 5% SP-2401; 1.5% OV17/1.95% QF-1; and 3% OV-1/6% OV-210/8% OV225). On the bests of coinjections of the standards with extracts from American (Aroclor) and Japa nese (Kanechlor) polychlorinated biphenyls (PCB), two of the compounds in those extracts have been identified as 2,3,7,8-tetra- and 2,9,4,7,8-pentachlorodibenzofuran. The concen trations of the compounds were estimated to range from 0.08 to 0.83 ug/$ of PCB. Vos et a). (1970) have identified toxic components of Eu ropean polychlorinated biphenyls (PCB) as two chlorinat ed dibenzofurans. Subsequently, several additional chlori nated dibenzofurans ware found in the German prepara tion examined by Vos et al. (Bowes et al., 1973). Further in vestigations have led to the detection by high-resolution mass spectrometry of those contaminants in American (Aroclor) PCB (Bowes et al., 1975). A recent study reports unidentified tri-, tetra-, and possibly pentachlorodibenzofuran components in Kanechlot 400 (Roach and Pomerants, 1074). Kurateune et al. (1972) have identified Kanechlor 400 as the agent responsible for Yusho, a toxic syndroma in humans who have ingested contaminated rice oil. The reported high toxicity of the chlorinated dibenzofu rans (Vos et al., 1970) end their presence in PCB have prompted synthesis of authentic standards and determina tion of their effects on induction of the enzyme aryl hydro carbon hydroxylase (Kanda et al., 1974). The present paper reports gas chromatographic characteristics of those stan dards, and the identification of two isomers in Amsrican and Japanese PCB based on co-injections of the standards with extracts from the PCB. (EXPERIMENTAL SECTION Bynthesle of Chlorinated Dibenzofurans. Authentic dlbenaofaran derivatives (Table 1) were synthesized by regioapecific methods and characterized by proton magnetic resonance and mas* spectrometry (Kende et al., 1974). Extraction of Chlorinated Dibenzofurans from PCB, and Quantification. Aroclor 1248 and 1254 preparations (obtained in 1969 from Monsanto) were pieced on Fiorieil columns, eluted in solvents of increasing polarity, and par titioned over alumina as described elsewhere (Bowes et a)., 1976). The latter separation yielded mixtures of chlorinat ed dibenzofurans essentially free of PCB Interference. Chromatograms of extract fractions resulting from use of these techniques ere illustrated in Bowes et el. (1975) for Aroclor 1264 end in Bowes st el. (1973) for Clophen A-60, a German PCB. Coinjections of authentic standards were made with one or more fractions recoversd from ths Fiorieil column (end passed over alumina) for each PCB. AU chlori nated dibenzofurans usually were found in the first thrse fractions. Once coincidence of authentic dibenzofuran peak with extract peak wee established on ths four GC columns (described below) for one or more fractions from each PCB, isomor concentrations were estimeted for each fraction by assuming s peak having the same retention time as the dibenrofuren isomer is thst compound, and summing the concentrations for all fractions if the peak occurred on the chromatogram (the OV-1 column was used for this basis of comparison). Compounds were quantified with the use of standard curves based on injections of different amounts of the appropriate dibenzofuran isomer. For the present study, the same extraction and partition ing techniques were applied to Kanechlor 200 and 500. Compounds having the seme gas chromatographic rvie*. tion times on the OV-1 column as compounds identified previously by mass spectrometry as chlorinated dibensofo. tens in the Aroclor PCB were isolated as mixtures Im from ths Japanese PCB. The ges chromatographic tech* niquea described for the Aroclor extracts (co-injection and quantification) were used for the Kanechlor extracts. Gas Chromatography. Concurrent with the fftrexew* analyses, 16 chlorinated dibenzofurans containing frwa three to six chlorine atoms were injected into gas chrome* tographs having electron-capture detectors. The retention times relative to dieldrin were carefully determined (*t%l on four columns of different polarities (Thompson st 4. 1969; Canada, Department of National Health end Wei* fare, 1973). Instruments and chromatographic conditions ere listed below: (l, Micro Tek 220); (a) column: 3% OV-1 on lOiMa mesh Supslcoport, 6 ft X 4 mm i.d., glass; (b) detector. 3Ni; (c) detector, inlet, and oven temperatures, 273, !& and 195*, respectively; (d> column How: 50 cm'J of N^mim (e) purge flow: 65 cm9 of Na/tnin; (2, Micro Tck 2201: (et column: 5% SP-2401 ( QF-1, Supelco, Inc., BellefoM* Pa.) on 100-120 mesh Supslcoport, 6 ft X 4 mm i.d.. gU* (b) detector: 3Ni; (c) detector, inlet, end oven tamper*- tures: 273, 226, and 200*, respectively; (d) column flow: 66 cm9 of Ng/min; (e) purge flow: 55 cm3 of Nj/min; (3, Vnhen 1440): (a) column: 1,5% OV-17/1.95% QF-1 on 100-131 mesh Chromoeorb W, acid washed, DMCS treated, 6 ft x 2 mm i.d., glass; (b) detector: 3H; (c) detector, inlet, end wea temperatures: 225, 230, end 192*, respectively; (d) column flow 35 cm9 of Nj/min; (4, Varian 1440): (a) column: 3* OV-1/5% OV-210, 5 ft + 3% OV-1/6% OV-225, 0.3 ft on 60-80 mesh Chromoeorb W, acid washed, 4 mra i.d., glam; (b) detector: 9H; (o) detector, inlet, and oven temperature* 232,220, and 213, respectively; (d) column flow: 40 cm3 nt Ng/mtn. RESULTS AND DISCUSSION Retention times of the 15 authentic dibenzofurans rele- tive to dieldrin ranged from 0.68 to 5.37 (Table l); three are within the range of retention times of the common chlori nated pesticides and PCB. The gas chromatographic pa rameters are the same as those used for the pesticide* and PCB. _ Individual coinjections of 2,3,7,8-tetra- and 2,3,4.7.8pentachlorodibenzofuran with fractions isolated from Aro clor 1248 and 1254 and Kanechlor 200 and 500 showed co incidence of isomer retention time with peaks in the frac tions on all four columns, with the exception that on OV- 17/QF-l the 2,3,7,8 compound eluted in an unresolvrd re gion between two large peaks in the Aroclor 1254 fraction. The retention time of 1,3,6,7-Utrachlorodibenxofuran .*bo coincided upon coinjection with that of a peak in the '*** lates from all four PCB on the OV-1 and SP-2401 column*, but definitive peak matches on the other two column iyv 1*22 J, Aorfc. Food Cham.. Vol. 23, No. 6. 1975 MQNS 087303 I'elllc 1. C,e Chromatograph Retention T/me of Authentic Chlorinated Dlbenzofurans Kctatlvo toDieldrln Column Structure of compd OV-I SP- OV-17/ OV-!/ 2401 QF-1 210/225 lie ratenidentified ibmoftiurw eles ihlc techctlonend :le. tangoing Ini from i chromeretention ed UM| ion et el., end Wel- ere lleted n100-130 detector 373, 230, >f Mi/mln; : 220): (e> Icllttante, i.d, glue; temperonflew: 00 (3, Verlen i 100-130 1,0 ft X 3 end oven I) column lumn: 3% 0.0 ft on 1.d., ilece; lieroturet: I 40 cm* of irane relnillieeeere ion chlorlraphlc pe.Iddee end 2,3,4,7,0from Areihowed co n the free st on OVeolved re tt flection, ifuren elso In the leo1 columno, ilumn eye- 2,3,8-Clj 2,3,6-Cl, i.M-cig 1,3,7,B-C1 1,3,6,7-C1, 2,3,6,8-Cl, 2,4,6,7-0. 2,3,7,B-C1, 2.3,6.7-Cl, 9,4,8,7-0, 1,2,3,7,8-Cl, 1,2,3,6,7-Cl, 2.9,4,7.8-Cl, 2,3,4,6,7-Clj 1,2,3,6,7,8-Clj 0.82 0.85 0.87 1.26 1.29 1.42 1.42 1.57 1.64 1.68 2.70 2.74 2.96 3.04 4.13 0.68 0.72 0.71 0.89 0.92 1.10 1.18 1.28 1.34 1.47 1.84 1.87 2.29 2.39 3.11 0.83 0.88 0.90 1.21 1.26 1.74 1.59 1.70 1.92 1.96 3.08 3.16 3.66 3.80 5.37 0.77 0.80 0.81 1.02 1.09 1.28 1.32 1.30 1.56 1.64 2.15 2.20 2.66 3.01 3.71 terns war# not possible because of interference from over* lapping peaks. On the beeie of the procedures described, 2,3,7,8-tetrachlorodibeneofuran (I) and 2,3,4,7,0-pentechlorodibenzofuran (III) appear to be present in Aroclor 1248 and 1254 and Kanachlor 200 and 500. The presence of the 1,3,6,7 isomer (II) in the PCB cannot be considered established to the same extant The retention times relative to dieldrin on an 0V-1 column for a tetre- and a penUchlorinated dibenzofuran identified In Clophen A-60 (Bowes et al., 1973; note Figure 1, peaks B and E) are the same as those reported here for the 2,3,7,8- and 2,3,4,7,8*dibenzofuran isomers (Table I). a ci Cl 'Cl Cl' `a Amounts of chlorinated dibensofuran isomers calculated to be present In the PCB were estimated to range from 0.08 to 0.63 ag/l (Table II). Although there te no evidence that chlorinated dlbensofurane are present in wildlife, these date allow one to estimate their potential concentrations. If tha diksntofurans wars present In tissue in the same amounts relative to the PCB, the range of concentrations of tha dibtntofaran Isomers identified here would be approxi mately 25 to 250 pg/g fresh weight in Great Lakes herring gull (Larut argentatua) livers found to contain 300 ppm of PCB (Bowes #t si., 1973). Chlcka fed 6 sg/kg per day of 2,3,7,8-tetrachlorodibenaobran died within 8-15 days (Goldstein et al., 1974). The toxicity to chicks Is therefore simitar to that reported by Schwati et al. (1973) for 2,3,7,8-telrachIorodibenzo-p-dioxin. The latter compound is known to be teratogenic (Schwou et el., 1973); the teratogenic potential of the chlo rinated dibencofurens has not been established. Chick em- COM.Ml.NlrA HONS Tabic II. Concentration or Chlorinated Dibcnzofuran Isomers in PCB (ug/gof PCB) PCB Slruclure o( compd Arodor 1248 Aroctor 1254 Kane- Kanechlor chlor 200 500 2.3,7.8-CI, (I) ,2,3,4,7,8-Cls (111) 0.33 0.83 0.11 0.12 0.10 0.10 0 19 0.08 bryo bioassays have demonstrated that the ability of 2,3,7,8-tetrachloro- and 2,3,4,7,8-pentechforodibensofuran to effect induction of aryl hydrocarbon hydroxylase is comP`bja to that of 2,3,7,8-tetrach)orodibenso-p-dioxin (Kende et el., 1974); this property was characteristic of all polychlorodioxins tested (Poland and Glover, 1973). Our findings point to compounds I and III as poesible sourest of toxicity of commercial PCB. ACKNOWLEDGMENT We are grateful to Dr. Vos for providing samples of Kanechlor 200 and 500. LIIBKA1UKB C1I BU Bm#Bk0' n ' M Simoneit. B. R., Burlingame, A. L., Riiebrough, R. W., Nature (London) 25S, 306 {1076)7 "* Simoneit, B. R., Burlingsme, A. L., de Laooe, B. W. Rtabrough, R. W., Environ. Health Penpoct. foe, l/lil (1973). Canada. Department of National Health and Welfare, "Analytical Methods for Pesticide Residues in Pood", 2nd ed. Quanta' 7tU4w\?*?*da-N* H44-2M9. ravieed, 1973. Golds^in, J. A., McKinney. J. D., Lucier, G. V^,, Moon, J. A,, noC278*n(i9P74)B#r*man` Pharmaco(o*i*t l#* m (Abrtract K*nc^l A' S Wade, J. J,, DaCamp, M. R., Ridge. D., Poland, A., 167th National Meeting of the American Chemical Society. Los Angelas, Calif., April 4, 1974, paper ORON 130, mamiecript in preparation. Kuratsune, M., Yoshimura, T-. Matauxaka, J.. Yamaguchi. A.. En. vtron. Health Porxpoct. No. 1,119(1972). Poland, A.. Glover. R., Mol. Pharmacol. 1,736 (1973). 12 336 j]^Pom*r,nU`1 H -Buil Environ. Contam. Toxicol. Schweu, B. A^. Norris, J. M., Spsrsehu, G. L., Rowe. V. K., Geh- nng. P.J. Emerson, J. L., Gerbig, C. G., Environ. Health Per. tpcct. No. *,87 (1973). Thompson, J. F., Walker, A. C., Moseman, R. F., J. Auoc Off. Anal. Chcm. 52,1263 (1969). Vot, J. G-, Koeman. J H . van der Maas, H. L., tan Noaver da (J97oT' ^ ^ *** ^ Cotmtt. Toxicol, a, 626 Gereid W. Bowes*1 Michael J. MuIvihUI1 Mark R DeCamp1 Andrew S. Kendo1 * Canadian Wildlife Service Toxic Chemicals Section Ottawa, Canada KlA OH3 2 Department of Chemistry University of Rochester Rochester, New York 14627 3 Present address: California Water Resources Control Board Division of Planning and Research Sacramento, California 95801 Received for review February t3,1975. Accepted July 21,1975. Re search was supported by the Canadian Wildlife Service and NaUpnel Institute of Environmental Health Science# Grant No. ES00965 to the University of Rochester. MOMS OS73fl4 J. A0rlc. Food Chenrv. Vot. 23. No. . 1975 1222 BY A. KARIM AHMED The accumulation continues A. KARIM AHMgO U a jtalf scientist lor th Natural Resource* Oalansa Council in Naw York City. 6 POLYCHLORINATED biphenyls (PCBs) were first imroduced into commercial use more than 45 years ago, and for a long time the widely used industrial chemicals were considered to be relatively non* toxic. Their potential threat to the environment, however, was recog* nized in 1966, when the Swedish scientist, S. iensen. observed the presence of the compounds in fish and wildlife samples while analyzing for chlorinated hydrocarbon pesticide residues.1'3 Since that initial discovery. PCBs have been detected in numerous aquatic and animal species and have been found in high concentrations in industrial waste discharges, river-bottom sediments, food packaging materials, and in foods such as poultry , fish, and dairy products. Detectable levels of the chemical substance have been found in marine life ranging in size from small (plankton and zooplankton)3,4,s to large species (tuna).4 High levels of PCBs have been found in fish-eating and predatory birds.7demonstrating the process of concentration of the sub stance along the food chain from lower to higher animals.11 a process which unfortunately has become all too well known in the era of modern industrial and agricultural activity. Relatively large concentra tions of PCBs also have been discovered in me eggs of wild birds.4'9,13 During the past ten years, PCD residues have been analyzed in wild life and fish samples in Holland. Germany, and the Baltic Sea.7'13 Off the coast of Scotland, PCB residues have been found in several marine species, the contamination presumably having arisen from sewage wastes dumped into the open sea.14 Nevertheless, despite global inci dence of the chemical in the environment, residues are generally found mostly in regions of the world where there is intense industrial and urban activity. In the U.S.. PCBs in increasing amounts have been detected in the eastern and western coastal regions, in highly urbanized areas (for instance, in and around the Chesapeake Bay, San Francisco Bay. and Puget Sound), and in regions where industrial discharges are known to occur, such as Escambia Bay. Florida, and the Hudson River.*.'s.**.*3 The environmental accumulation of KC h residues continues despite attempts by both industry and the federal government to improve the situation. As will be explained, industry's countermeasures have been i tr% MOMS 007385 limited, and government action hits been hesitant. In the U.S.. the impact of reus on the environment is best illustrated by ever Increasing contamination of sport and commercial fisheries in ihc Gre.ir Lakes region and elsewhere. According to data from the Michigan Department of Natural Resources. Iwels of ecus in lake trout and Cnho salmon from Lake Michigan showed 3 sharply increasing trend since 1972. By 1974. the values ranged from more than 10 to nearly 25 parts per million (ppm), well above the present Food ind Drug Administra tion's (I da s) moximum. allowable concentration of 5 ppm for fish and shellfish.'1 In sharp contrast, DDT (avals in the same species of fish showed s declining trend since 1970, when DDT consumption in the U.S. was curtailed.* * Not only are the eco logical consequences of continued pc 11 contamination ominous, but (he poten tial economic implications are serious, tinea tha total annual value of sport fishing in Lake Michigan is as high as $46.5 million.'9 In addition, the com mercial catch of fish is now worth about 52.S million each year.20 Tha Michigan studies are supported by studies made by the Wisconsin De partment of Natural Resources. Fish samples collected in 1974 showed ex tensive contamination.11 Affected types included Chinook salmon, Coho salmon, brown trout, tiger trout, lake trout, whltefiih, and carp. Centrally, tha residue levels ringed well above 5 ppm, with lake trout (up to 43.6 ppm) and carp (up to 51.6 ppm) showing tha highest concentrations. In tha Uppar Fox River, ample* taken at one station by Wisconsin re searchers in 197$ showed high concen trations of pcbs in white suckers (32.7 ppm), carp (average 35.9 ppm), and northern pike (average 15.4 ppm). Sampiea from several areas of the Mis sissippi (Uver snsiyted by the depart ment in 1973 showed similar residues of PCBs in walleyed pike, lergemouth ban, northern redhorse, and carp. An Interagency task force on pcbs, formed of federal and several'state agencies of Minnesota and Wisconsin, tempted fish in tha Mississippi River during the early summer of 1975 and gain found similar levels of pcbs in several fish species.11 Elsewhere, the Division of Fish ind Game of the Commonwealth of Massa chusetts has in the paet detected high PCI levels in fish in several rivers and siraama in tha state.11 From other data collected by tha agency, it is clear that in 1972 there was extensive con tamination of a large variety of fish species in nearly all the rivers which wart ampled in tha stole, with mean environment, voi. 11. No. 2 STRUCTURE OF PCSS Polychlorinetad biphenyls (pets) is a generic term used for a number of synthetic organic compounds that possess the fol lowing chemical structure: C> Ci ci Cl pc es are a mixture of different chlorinated biphenyl homologs (very ciosoly related chemical substances). Thus, different PCt formulations or products may contain mix tures of biphenyls which have different percentages of the many possible chlorinated homologs, each containing a dtffarant number of chlorine atoms per biphenyl molecule. Monsanto Company, tha sofa U.S. producar of pets, sails its product undtr the trade name Aroclor. This produet is sold under different formulations: Aroclor 1264, 1262. 1260. 1254. 1248. 1242, 1232, 1221, 1016. and so on. The last two digits in this biphenyl series denote percentage of chlo* fine in the mixture. Aroclor 1016 is an exception to this nomenclature, since <t contains 41 percent chlorine and is. In fact, very similar in composition to Aroclor 1242. Trade names used by foreign manufacturers include: Phenoclor and Pyrelene (Prooeiec, Trance), Kennecftlor and Santelfierm (Kanagafuchi Chemical Company and Mitsibushi-Monsanto, respectively. Japan). Clopheit (I. Q. Farben lndustrle A. (2., Germany), Fencior (Caffaro, Italy), and Sorol (U.S.S.R.). PCB residue levels ranging betwesn 1.11 and 197.0 ppm. To date, however, the most contami nated fish in the U.S. have been found in the upper reaches of the 'Hudson River, near and below two General Electric plants in the Fort Edward- Hudson Falls srea in ihe uppar Hudson Rivar more than 40 miles north of Al bany. The two plants manufacture electrical capacitors in which pcbi are used as insulating fluids, (n 1974, sampling by the U.S. Environmental Protection Agency (epa) showed yel low parch and shiner minnows to con tain average pco residues of 17 and 78 ppm, respectively, with one rock bass iimpis containing 350 ppm.14 It ap peared that the two General Electric plants had been discharging approxi mately 30 pounds of pens into the river each day; in recent months, this amount seems to have declined to less than 10 pounds per day. Fish samples collected in 1975 by the New York State Department of Environmental Conservation confirm the earlier find ings. The composite pcu averages in fish caught near one plant show typical values well above 20 ppm, with one American eei sample yielding residue values of 403.4 ppm (concentration measured as Aroclor 1016/1242).11 As large amounts of pcbs ware being discovered in the upper Hudson River, New York State Department officials also were finding high residues of pcbs in fish species of recreational and commercial importance farther south in the Hudson River.11 Striped bass caught near tha Albany araa showed total PCB residue values of between 11.08 and 89.76 ppm. Fish caught in the lower reaches of the river had a relatively higher concentration of sn older PCB formulation (Aroclor 1254), indicating long-range transport of pcbs discharged by industrial activi ties in the past. Striped bass sampled near the West Point and Tappan Zee area of the Hudson River (30 miles north of New York City and several hundred miles south of the Fort Edward-Hudson Falls ares where the Gen eral Electric plants are located) had total PCB residues of from 1.16 to 7.54 ppm. Similarly, a sample of American shad in the Poughkeepsie area showed PCB residua levels of 9.0 ppm. Disruption of the striped bass com mercial fishing industry on tha Hudson 7 HONS 087386 Hi*i ( NCc hn tt*n in *qu*Ut River would have serious economic consequences, since [he value of the annual commercial catch appears lo he about SI.2 million/4'11'*" in addi tion, tile annual take of striped bass by sportsmen exceeds the annual commer cial catch,,N luinliermore, the overall problem is serious m its (elution to re production hi striped bass. The striped hats is a migratory fish which has slock dial intermingles in various locu tions such us the Chesapeake Bay. the Delaware River, and the Hudson River regions. As a result, tvii contamina tion may affect u large segment of the entire North Atlantic stock of striped bass. Bottom Buildup Of equal concern is the accumulation of IVlts in river-bottom sediments. K ill, like most chlorinated hydrocar bons. are highly insoluble in water and tend to settle and then be adsorbed on silt and line panicles on the bottom.' * Ojia collected by the U.S. Geologi cal Survey icsus) on the Hudson River during the years ld7Xand 1^74 show the presence of i\ us in the water and in die bottom sediments of the river.'v Values ranging between OJ and .7.0 parts per billion (ppb) tv us have been reported in water sam ples collected at several stations on the Hudson Kiser*. The sampling sites in clude locations neur Poughkeepsie, Waterford. C helsea, and Khineheck. In contrast to water samples, ivn concentrations analysed from the river- PCBs, like most chlorinated hydrocarbons, are highly Insoluble in water and tend to settle and then be ad sorbed on silt and fine particles on the bottom. bottom sediments showed considerably higher values characteristic of the insol uble nature of tails. The US(Jt> data are summarized below:1* ri ll Concentrations in Hudson River Sediments. US<>s> Date Station tv n in Sediments (ppb) 7/74 Chelsea 7/74 Poughkeepsie 7/74 Waterford 7/74 Winebrook Hills `7/74 Chelsea M/74 Poughkeepsie 0/74 Wuterford 8/75 Roger's Island, south of Glenn Kalis 7.200 11,000 13,000 01 1,800 3,600 640 18,000 Mure recently, the i:>'a conducted water and sediment analyses lui'ivus in the vicinity ol Ford l-.dward. New 'lurk, near one of the General Llectiic plants. Water samples collected directly south of the plant's waste-water dis charge pipes had KB values of 2.2 to 3.1 ppb. Nearby sediments, in contrast to the water, contained 540.000 to 2.y&0.000 ppb (S40 to 2,V80 ppm), with 6,600 ppb being detected several miles downstream of the discharge pipes.14 These concentrations obvi ously arc much larger than those at the more distant sites checked by nsc;s personnel, wen (hough the latter con centrations are themselves excessive. One immediate practical problem is that the largest concentration ol ivns is likely to exist in the deep navigation channel of I he Hudson, and dredging in tins channel will further disperse the material.* * 'J0 Toxic Effects of KB* Based on (tie high lethality ut rctts lo marine and Ircsliwaler aquatic species, (lie National Academy of SciencesNational Academy of Lnginccnng Committee made (he following recom mendation:' 1 "Aquatic life should be protected (that is. sale liom toxic cffcctsl where the maximum conceutiaiion of total IV U in mtlillercd water does not ex ceed 0.002 micrngram per liter 10.002 ppb I at any lime nr pi.ice ,m.l the resi dues in Hie general body iisoios ol any aquatic organism do not exceed 0.5 micrugr.im per gram [0.5 ppm|." These levels obviously jre exceeded m areas ol the HuJson River and else where. I he danger to aquaiic hie is a warn ing ol the danger to human life. In tact, the toxicity ol ivin to humans has been cleaily and tragically demon strated In IVON a severe form of skin disease was diagnosed in Japanese fami lies who consumed rice oil contami nated with Kjncchlor 400 (IV U with 48 percent chlorine content)/, J 1 The disease, known as Hie "Yusho syn- diome," is characterized t*y swelling of the upper eyelids, visual impairment, acne-like formations, and heightened pigmentation ot the skin/1 and a total of 1.057 poisoning cases have been re cuidcd lo date m Japan/1 Patient* with this disease also have exhibited neurological disorders and have shown signs of hearing loss. Brfties born to several patients had many of tha symptoms ot the disease, indicating a placental transport of ivus. most let uses of (he victims were smaller titan the national average Another dis turbing feature of (he disease was the observation that most patients recov ered very slowly, which suggested that iv us weie retained in Htcir bodies over a very long period." n its have been detected in human adipose tissue (con nective (issue m Hie body containing stored cellular I a t > in such widespread occurrence that over 40 percent of the U.S. population contains one part per million or more/4 A number ol studies have conclu sively shown the effect of iv its on the reproduction processes of some bird* and animals, including mon key s/1 '5'J0 *1 * 4U It is impor tant to note that iv us with lower chlorine content may have a greater etlect on reproduction Hun biphenyls with higher chlorine content, even though the lornier substances are now being sUggc-Nled as cuboiloles for the latter. In a recent review article oti the toxicology ol iv us, Kcnair Kimbrough ot Hie ( enter tor Disease Control ill Atlanta. Georgia, slated: " " I lie rcsiills obtained liom Hie re production studies in birds pailicularly seem lo indicate Hut Hie lower chlori nated biphenyls all eel icpioduct ion more than Hie higliei chknmaled bi phenyls. and it is veiy unpoil.iut tu de- Iciminc >v lie (lie i Hie lowci chloi mated biphenyls that have been suggested as replacements for prcsenil) employed chlorinated biphenyl' have an eltcct on Mann 1974 MGNS 087367 reproduction." The recent pea toxicity ten* In monkeys art particularly relevant to human health considerations. In en ex* tensive series of tests carried out by James Allen and hit colleagues at the University of Wisconsin School of Med. Icine, t'CUi in the diet of rhesus mon keys caused sitniflcant effects thut mimicked both the symptoms of known human toxicity and rcproduc* tion failures in experimental animals. When female rhesus monkeys were given 23 ppm of Arodor 1248 for a period of two months, severe symp toms of facial swelling and skin erup* lions were manifested. 1 At lower die* lary levels (3.0 ppm and 2.5 ppm) of the same substance, similar clinical symptoms ware observed efter a few months; more significantly, these low levels of fOs had a marked effect on reproduction. After three metings with mete monkeys, only 12.5 percent of the 5 ppm pea dietary group and 57.5 percent of the 2.5 ppm group were pregnant as compared to 90 percent pregnancies in e comparable control group.'* At the tame time, offspring were significantly smaller In site; their health was further threatened since they continued to ingest high pcb levels from the nursed milk of their mothers.*0 One notable consideration related lo the experiments in monkeys li that the present PDA tolerance limit of 5 ppm*1 * for PC* residue in fish end shellfish is based on the aisump. tion that toxic effects occur it levels much higher than it actually the cue. On this beets, then, the pda tolerance limit U too high. Also, of serious concern is e recent study oonducted by e group of re search investigators it the Center for Disease Control in Atlanta, the upa, the National Cancer Institute, end the Johns Hookins University School of Medicine.*' They observed that when experimental female rats wars fad a diet containing 100 ppm of PCS (Aro dor 1280) for about 21 months, 26 of 114 of the experiments! animals exam toed hid malignant liver tumors-(Hepa tocellular carcinoma), whereas only I of 173 control animals had the disease. At the same time, 146 of the experi mental and nona of tha control ani mals had tumorous laeions (neo-plastic nodules) in the Urn. Other effects of pcbs that have been reported in Die scientific iiureture include; (I)increased production f certain ensymes in the livers of hu man beints end laboratory rate, (2) in duction of liver porphyria in several animal species, (3) interference with the immune defense mechanisms in rabbits, (4) neurological disorders in rate, (S) increased t'cu residue in fatty Bnvtrenmem, Vot. IS, No. t tissues, serum, and milk, and (6) toxic effects in chick embryos.41 ** There has been some concern that reported i'('u effects may be attributed in part to the presence of chlorinated dlbenxofurans as a contaminant in ITU mixtures.1' Chlorinated dihenzofurans have been shown to he acutely embryotoxic and have been detected in sew ersi pcb preparations K'lophen A 60, Phenoclor DP-6, Aroclors 1248, 1254, 1260).** Recent reports by M. Kuratsune and his associates have Indicated that the "Yusho" patients apparently hid been exposed to reus in rice oil contaminated with chlorinated dibenzofurans and showed detectable levels of this compound in thetr body tis sue.** However, it was not determined from Uus study whether the contami nation occurred during manufacture of the PC as or during ihe use of the re a mixture as e heat exchange fluid in the rice oil plant, since high temperatures may have led to its formation through the hydroxylation and oxygen ring bridging of chlorinated biphenyl mole cules. At present, the possible link of PCB toxicity to the presence of chlori nated dibenzofuran contaminants re mains highly speculative, as there ap pears to be no direct experimental evidence that dibenzofuran derivatives have .long-term chronic effects simitar to those which have been amply dem onstrated with fCBs." '** Control of fCBs The attack on pcb contamination has taken two forms, one a voluntary re sponse by manufacturers of the sub stance and the other e response by var ious government bodies. Both re sponses have been inadequate, it will be shown in whit follows. In 1971, over 106 million pounds of PC Be was produced in the industrial countries of the world, with e third of this, nearly 40 million pounds, being manufactured in the U.S. 1 During the late 1950s end into the 1960s, U.S. domestic sales of pcbs increased nearly threefold, reaching e peak of approxi mately 72 million pounds in 1970.** ftior to 1970, about 60 percent of PC B material sold domestically in the U.S. was used for closed electrical systems such as capacitors and trans formers. Another 25 percent was used as plasticizers and in the production of carbonless duplicating paper.** In Sep tember 1970, Monsanto Company, the sole manufacturer of pcbs in the U.S., restricted its sale of pcbs because of environmental contamination by the chemicals. This restriction consisted of limiting sales to those materials ear marked for closed electrical systems. Thereafter, U.S. consumption was re duced considerably. It is important to note, however, that these reductions occurred mainly in the use of PfUsas plasticizers and as li>draulic and lubri cating fluids, since the bulk of pcbs (60 percent), as mentioned aboyp, had been used in electrical systems. This chemical substance is still being used almost exclusively as the insulating fluid for large, high-voltage capacitors (as well as for certain small ones) and for electrical transformers. In addition, the EPa estimates that approximately one-half million pounds of pc Us is being imported into this country each year4* and presumably is being used in products other than electrical equip ment. As to government response to the PCD problem, a federal Interdepart mental Task Force was convened in 1972. The poup concluded that be cause of the highly persistent nature of PCBs and their bioaccumulation in ihe food chain, these chemical compounds posed e serious threat to human health. The group recommended re striction of the use of Peat to closed electrical systems such as electrical transformers end capacitors.** How ever, since Monsanto Company actually had already begun restricting domestic sales in this fashion, it is not clear whether the task force's recommenda tions, issued a year and a half after Monsanto's action, had any influenca on the company's decision (although this has recently been suggested by a federal official). 0 In July 1973, the fda established PC a tolerance limitations in a variety of food products, as follows;*1 FDA Tolerances for PCBt in Food and Food Packaging (ppm) Milk* Dairy products* Poultry* Fish and shellfish** Eggs Infant and junior food Complete and finished animal feed Animal feed components Paper food-packaging material 2.5 2.5 5.0 5.0 0.S 0.2 0.2 2.0 10.0 *On fat basis **Edible portion Toxicity data obtained during the past year showing severe reproductive failure with low concentrations of pcbs in primates (3.0 and 2.3 ppm) and the recent demonstration of car cinogenicity with rats**'41 indicats the need to substantially revise the present i oa tolerance limitations of PCi)s in foods. Although the present tolerance standards are deficient, the I DA his in recent months taken sei zure action based on these standards 9 HONS 087388 against several fish shipments ear been introduced in the slate legislature marked lor commercial markets in Luke Michigan, since t'cu concentra to place strict control on the use and sale of pcus in Michigan.*1 tions in the fish exceeded the present In Wisconsin, the Division of Health 5 ppm guideline.*1 Stmilurly, the mi a seized a shipment of carp this summer in Lake Pepin on the Mississippi River.*3 in view of a recent legal de of the Slate Department of Nuiurol Resources has issued warnings on con sumption of large lake trout and salmon from Lake Michigan and the cision (hat apparently allows the J;I>a upper Mississippi River. In August to define pesticide residues in foods as 1975, the department held a hearing an indirect food additive, the ri)A is with a view to developing a strategy to expected to enforce its guidelines more control the sale and distribution of forcefully in the future, pda officials in the Great Lakes region have warned VCDs within the state.*1 In Minnesota, an Interagency Task Force was estab that shipment of chubs, Coho salmon, lished, principally to broaden the mon and take trout may be disallowed m itoring of pc Us in fish in several rivers interstate commerce, since the fish and streams in the state.33 continue to contain high residue levels In terms of administrative remedies, of I'CHS.*1 It is apparent that with a the strongest action was taken this more thorough monitoring and surveil year in New York state, after it was lance program, many species of fish in discovered that the two General Elec the Greet Lakes region and In several tric plants on the Hudson River ap rivers in the East Coast area will be essentially unavailable for human con sumption for many years. One of the great ironies of the pres Uf| amount* or pent hi ha round In lltn in in* Hueton Alvar, *oekaily in tnoM o< roer*atlon*l and commarcUl *. ent situation is (hat more than three yean ago the Federal Water Pollution Control Act (kwtca) directed the fed eral government (specifically the F.PA) to take swift action lo reduce the dis charge of i'CBs and other toxic water pollutants to safe leveU. The fact that today there is no meaningful national program to regulate t'CB discharges is a result of the federal government's fail ure to carry out the act as written. The congressional authors of the tu'PCA believed that the "hazards posed by toxic substances" made their effective regulation "especially up gent."*1 Accordingly, they established in the act a "national policy that the discharge of toxic pollutants in toxic amounts be prohibited"*4 and added to the act a far-reaching special pro vision, Section 307(a), to ensure that this goal was fully implemented. If the section's mandatory deadlines had been met, toxic pollutant effluent standards covering I'Cbs and other toxic polite tarns would have been promulgated by the kva roughly two years ago and compiled with by dischargers about one year ago. Yet, to date, the EPA has failed to promulgate a single stem durd under this provision. Despite shortcomings in federal en forcement, several states have taken ad ministrative and legislative initiatives to control the discharge of pc os into lakes and rivers. Earlier this year, the Michigan Natural Resources Commis sion endorsed the recommendation of the Uike Michigan Toxic Substances Committee, calling for a ban on hcd imports and their use in the U.S. and for a rapid replacement of pc us in electrical capacitors and trans formers.*1 At the same time, a bill has10 10 peared to be (lie major dischargers of pc us in upper regions of the river. On September 2d, 1975, the New York State Department of Environmental Conservation issued an abatement order requiring the General Electric plants to achieve zero discharge of pc ns by September 30, 1976. Admini strative hearings were begun on Octo ber 6, 1975. * At the same time, Ogden Reid, commissioner of the d partmem, publicly warned consumers against eating striped bast from the Hudson River and salmon caught in Lake Ontario.** On the international front, the Or ganization for Economic Cooperation and Development (OECD) a few years ago recommended that its member countries which are involved in PCI production (including the U.S., West Germany, France, the United King dom, Japan. Italy, and Spain) restrict the commercial use of PCfts to closed systems.97 Only Japen has taken fur- thrr Uriel measures to completely tllmimitf the use ol I'CUs in uU atm- 12. Graicnua, V.A., A. Orcicnus, and R.j, CmericK, "insecticides, Polychlorinated Blenanyit, and Mercury in Wild Cormorants, Bttrcial applications, including capaci tor* and transrormers. Japan also pro* Pelicans. Thair Ee*i, rood, and Environmam," dull. Envir. Csaom. Toxicol., 9:321, 1973. Mbits the import and export ol the compound, and, since September ! 972, Ultra lias been a virtual elimination of almoM all applications of I'CDs in that 13. KoomiA, J.H., M.c. TcnNoevar. and R.H. Oavot. "CMonnaiod Diphenyl* m Fi*n, Mussels, and Biros irom in* River Rrn* ano tna Nan*,ino Coatial Area." Nature. 22111120, 1969. country,10 Most recently, following the Na* 14. Holden. A.V., "Soorca ol Poiycniorlnaiad Blonanyi Comamtni.o >n in Manna Environment," Naiura, 279 1220, 1970. lional Conference of reus which was 19. Maryland Oeol. Nai. Ret. and westing, held in Chicago on November 19 lo 21, 1975, the Ki'A on December 22, nous* El*e. Co., Chester River Study. An napolis, Md.. Nov. 1972. 1975, announced a I'ur-roaclimg federal 1G. Stalling, O.L., and ft.L. Mayer, "Toxieit'ti ol PCBs lo Fun and Environmental policy of '`totally eliminating the use RatiOwet,'' nvtr. Health ftertpeet., 1:199. of polychlorinated hiphenyts (ri iis) as 1972. rapidly as possible" in the IKS.**'I5.** 37 * *-1>17r.0., Dil",uAka,ftoTi.yWc.h,ioJr.lIn, aLiaoow*,BiaonndenAy.iJ, WHion, (Arocior In more specific action, the i: pa has 2294) in me Water. Sediment, and Biota of ordered the two General Electric plants Etcemeia Bay, Florida." Bull. Envir. Con* tin. Tomcat.. 9.in, 1970. on the Hudson River to achieve zero 19. Hatta, J.L.. CoPtamlnmtt in Ortai uurt discharge by June 1977.** it is dear ftlth, Michigan Oaoi- Nat. Rat. Staff Raport. from these actions that the federal gov* ernment has recognized the gravity of the PCII issue and at last has taken definitive steps to address the problem. June 1979. 19. Michigan Dapl. Nat. Rat.. Michigan Gnat Lakes Trawl and Salmon Fishery, 1949*1972, ftimenai Mgmi. Raoort No. 9, Jun* 1973. 20. Haaca, j.l., and N. fogia, Fishery Olv., The title of this article as originally submitted was "4 Review of Federal end Stale Government Roles in Con* trolling Impacts of PCBt on the Envi ronment. " The Publisher and Editors of Environment arc responsible for the published titles and subtitles, selection of photographs and lead-in excerpts, Michigan Dael. Nat. Rat., erivat* communicanon. 21. Oaaurt*. P.. no v. Owtar, Cmormatad Hydroaareon Residua* in ftlth Irom Major Waiart of Wisconsin, witeontin Oapt, Nat. Rai., Bur. ftlth and Wildlife Mgmt. Report No. 79, Maolaon, wit.. July 1979. >2. intaragancy Tatk Fore* on PCBs. ftrailm* Inary Report en IN Mlyehiorlnatad Bl* phanylt In Mississippi Rlvar and Lake ftaeln. Minn. Poll. Com. A*., St. Paul. Mmn.. Awe. 1979.' photo captions, and preparation of most graphs and illustrations which appear In Environment articles. 23. Palermo, P.J.. Preeraaa RapoH. Maataenuiatu PailleldP Monitoring Program, April I, 1972 t# March 3t, 1973, Div. ftithanat and Gama, Commonwealth of Mar*. Borton, Man.. 1973. NOTES I. .Soman, S.. "A N*w Chemical H*i*ra," New My*tut, stitia, tees. I. WISSUAi 0., "Possible mitrfirtne* by ClUwtnetftO Biphenyls," Jour. Attn. Offi*. ami. asoi*.. seiioee, 1997. 3. ftHebrough, R.W., el !., "PCB Residues in Anemic Zoodianhion," Bull. tisvir. con* tam. Temeei.. lises. 1972. C.eim, Cl., at *1., "CMsimllid HvtfKtrbom m Plankton non* in* Gulf or momco an# Nwlhirn CinSCun," Bull. Envir. Con* loo*. Toniui., sisre, ten. I, were, O.M., ana ft.ft. Addison, "pcb ftotlduot in Plankton from ma Gulf or si. Lawrence," Nature. 246i919, 1973. e. rune, v,, p.m.k. cnot. -pcb ana Other induitrlai Haieeenalte Hydrocarbons in me environmani," run. lie*. Be. of Can* aBa Technical ftaeort <7a, ie7i. e. 1. 7. Jantan, 1.. at at.. "DOT ana PCB in Marina Amman iron* Swaaian waters," teaiere, 214:247, IStB. B. Waabtomh, B.W., at al,, "Polychlorinated Biphenyl* m tna Global Ecosystem," Nature. ttoiioee, itee. #. ftmii, i,, N.W. Moor*, and o.j. jetfrtas, "Pdtvehiorinataa Biphenyls m wild Biros in Britain and tn*ir Avian Toxicity," Cnvir. hew., tiS, e?o. 10, Kotman, J.H., "PCB in Mammals and Bird* In ilia Netherlands." PCB Cni*r*na It, B. Lundtubtn, *d.. National Sw*d. Envir. Brel. Ud. Pub. 4g, 1972. . sa il, Watar OuatMV CM aria. Raoort o* tna Commitiaa on wiiar Quality CMarie, Env. Studies Bd., NAS-NAC, Washington, D.C., i ere, 24. Nadeau, R.J., and R. Davit, Invettigatlon at Poiyahierlnatad Blphanyii In me Hwoton Rlvar: Hwdian ftalla*ftert Edward Area, EPA, Region It Report, 1974. 29. Bur. Envrr. Proi., CMv. ftlth and Wildlife, New York Dapt. Envir. CAhtarv., Mastering ef PCBt In Pith Taken from the Hudten River, Aipany. N.Y., Oct. 1979. 26. National Marin* Fltnariat S*rv., U.S. Oapt. ef Commerce, Pltnertat Statlttlci or tfta united StetM. 1971. 27. Deuel. D.G., 1970 Salt-Water Ans'lng Survey, NOAA, National Marine Flrfiana* S*rv,, U.S. Oapt. of commarca. Currant ftlahary Statlilici No- 6200. 1973. 26. Contend*!** Cdnon Co. of New voru, Inc., Final Environmemal impact SUtamant, Operation of Indian Point Nuclaar Ganaratlne Sfaiion, Pap. 1979. 29. Turk, John, U.S. Geological Survey, Albany, N.Y., privata communication. 30. Mtrnton, Thomai, wattmgnouia ocean Rasearch Lab., AnnaoeiU. Md.. prlvtia com. munlcttion. Alio, prelim, draft UOPar Chatapaaka Bay uudy. 31. Kimbrough, R.O., "7h* Toaleny of Polycnlermated Polycyclic Compound* and Related Chamicaii," CRC Critical Review* in Tonlapl., j*n. 197, o. 44ft. 32. Kurattun*. M.. *t al.. -'An Ep'damtoioai. cat Study on 'Yutho* or Cnioropipnanyi* Poltoninp," Pwkwoka Acii Mad., 60:913, 1969. 33. KuraUuna. M,, at *i., "Eeidamloioeicai Study of Yutho, a Pollening cawiad py inaatlion of Rice OH Contammatad w<m a Commercial Brand el Polychlorinated Bl* pnanyil," Envir. Haalth Parapact.. Apr. 1972. 34. Price, H.A., and R.L- Welch, "Occur rence Of PCBt in Humini," Envir. Haim Parrpact., Apr. 1972. 39. Pfatonow, N.S.. and l.h Kamaa. "Oia* tary Elfaeti of Poiychionnattd Bipnattyi* on Minu,'* Canadian Jour. Comp. Mad.. 37:391, 1973. f 36. Damgran. R.B.. R.L. Linear, mo C.W. Carlton, "Pulychtorinalae BrOhanyll: Th*ir Kffacir on Panned uneatenti," Cnnr, Haaim Panpeat.. 189. 1972. 37. K(Kia*'. M L.. O.C. Fanchar, gna J.C. Ca'andra, 'Tovicoieqic Siudiat wiin Poiy enronnafad Biohenyit," Toaicoi. and Appi. Pharnucot.. 19:407. 1971. 36. Allan. J.R.. L.A. Cantent. and O A. Barvotl*. 'flanduai Effactt of Snon-Taim. Low Laval Exposure of Nooiiumni Pnmaiat io PotyciMprinatad Bionanyit." Tomeal. and Appl. Pharmacol-. 30;J40, 1974. 39. Allan. J.R.. "Reioo-'S* of th Nonhuman Primate 10 Poiycniormaiae Bipnenyt Exoosura." ftadaratlan Fraeaadings, 34:1679, 1979. 40. Allan, J. R., Reg. Primate Rat. Ctr . Un<v. of wi*. Mao. Sen., Madison. w>s., pnvat* communication, 41. Federal Register. 36(129): 11096. July 6. 1973. 42. Kimbrough, R.O., el el., "induction of Liver Tumors in Sherman Strain Pamela Ran by Polychlorinated Bipnenyi Arudo' 1260," preonnt of tluoy ootamed Irom R.D. Klnsbrough. Clr. lor Onaete Contr , Atlanta, G. 43. Interdepartmental Task Fgret on PCBi, Polychlorinated Blpnanyli and the Environ ment, Washington. Q.C., May 1972. 44. Allan, J.R , and O h. Noroack, "Poly chlorinated Bipnenyi and Terohenyi.inducao Gastric Mucosal Hyoemiatia >n Primatat," SCianeo, 179:496. 1973. 49. Bowes. G.W., al pi., "identification of Chlorinated Dibenrofuran* m American Poiychtormateo Bipnanyis." Nature, 296:309, 1979. 46. Kurattun*, M.. v. Mesude. and J. Nag#- yama, "Soma of m* Raeam Findings Con cerning Yuiiie," paoor pres at Nat. Coni, on Poiycnior. Biohanyis. Chicago, ci,. Now. 19-21. 1979. 47. Environment Directorate, Org. for Econ. Coo*, and Davai.. `Poiycnnninaieo Bi phenyls: Thalf Use ano Control," Pans, Nov. 1973. 48. "Poiycmorinaiaa Biohanyis -- Environ mental Impact," Review by Panel on H*<. araeu* Trace Suottances, Envir. Res,. 9:249, 1972. 49. Train, RussaM ., admin., Envir. Prot. Ag., in background writtan statement ores, at Prats Conference on PCBt, Washington. O.C.. Oac. 22, 1979. 90. Scnw#ii2*f, g E., oir. on. of Toi< Sub stances, Env. Prot. Ag,, in statements mao* at nearing on PCBt held by Wit. Dapt. Nat. Rat.. Madison. Wi*.. Au*. 29. 197*. 91. Haste, J.L., "Summary of Ragu'aiory Cffortt of in* Graat Lakes Region Toward the Environmental Control of PCSs (Polychtortntied Btptsenytt)," tpaacn pros, to Governor's Graat Lakes Regional mtardisClpiinary Pasticid* Council, Chicago, ill.. S*pt. 19, 1979. 92. "Monoaia, HHH Center PCB Fray," Minneapolis Tribune, Aug. 26. 197$, e. jb. 53. Senate Raoort, No. 92-4 14, 92nd Con* grass. 1st Session, 1971, 0. 61. 64. Till* 33 Unllto ftttlet Code. 91291 (a)(3) (FWPCA S101 (a)(3); S307 (a)(4)) 95. New York Stale D*DI. of Envir. Cons., complaint issued igamtl General Electric Co., File No. 2133. Seel- 23. 1979. 96. "Slate Says Some Striped Bats ano Salmon Pose a Toxic P*m," New York Times. Aug. 6, 1979, p. 1. 97. Org. tor Econ. Coup, and Dtvet.. De cision of in* Council on Protection ef the Evlronment by Contrai of POlyaniorinatad Biphenyls, eooeied Fab. 13. 1973. 96. "Train Announces Plan 10 Control PCBt." Envir. Prot, Ag.. press release, Wash ington, O.C.. Dec, 22, 1979. 99. Fry*. Richard, legal steif. Env. Prof. Ag.. Region 11, New York, N.v,. privet* com munication. Environment, voi. IS, Nd. 2 11 MONS 087390 BV JOSEPH HIGHLAND JOSCPM HIGHLAND Is director of the Toxic Chemicals Program of the Envlronmentel Defense Fund In Washing ton, O.C. THE FIRST EVIDENCE that food supplies hud become contaminated with polychlorinated biphenyls (PC'Bs) was reported in 1966, when fish from various Swedish waters were shown to contain these chemi cals.' Since then, PCBs have been identified as contaminants in food supplies around the world. They have been found in pike taken from a lake in Finland, in mollusks and marine fish from Scottish waters, in a wide variety of fish caught in the St. John River system, in wildlife in California, and in trout and salmon taken from Lake Michigan.1*3 More recent findings indicate that contamination by PCBs continues to be widespread. Within the last few months, striped bass caught in the Hudson River have been found to contain as much as 90 parts per million (ppm) PCBs. while pike caught in the Baltic Sea were shown to contain 0.31 ppm PCBs in their muscle and up to 190 ppm in their ovaries.4*5 Moreover, plankton from the Baltic Sea, upon which many fish feed, contained levels of 25 ppm PCBs in their fat.4 The federal government currently conducts three separate programs in which the contamination of foods by PCBs is measured; the FDA (Food and Drug Administration) Pesticide Surveillance Program, the FDA Total Diet Program, and the USDA (U S. Department of Agricul ture) Surveillance Program. The FDA Pesticide Surveillance Program, which began in 1968, was developed to gather information on the levels of pesticides, as well as of PCBs, in foods and animal feeds based on a statistical sampling program designed to cover specific geographical regions of the U.S. Tlie program is intended to assure the safety of the human food sup ply by screening and removing shipments of foods containing pcbs or pesticides in excess of established tolerances. Commodities covered under this testing program include dairy products, eggs, fish, animal feeds, fruits, vegetables, and processed foods. In the FDA Total Diet Program, the levels of pesticides, PCBs, and trace heavy metals in sample diets are measured. Twice a month, a diet approximating that which would be consumed in a two-week period by a hypothetical fifteen- to twenty-ycur-old male is collected at retail stores in five regions around the U.S. Tire foods are prepared in the appropriate manner and then divided into twelve basic food composite classes, including meat, fish, poultry, and leafy vegetables. Each com* A' Pnoto from 8*|t*ndofC $<<! Poo**, tn. th >' '' ' ' <T MQNS 087391 What IS acceptable? petit* clan It then analysed for con* taminants. Th* US DA Surveillance Program eontiata of periodic aampiing and anal ysis of mttti and poultry for chemical oontaminanta, including pc at. Sampiet arc taken from federally impacted riaughlarhousss. Levels or PCBa In Food A aummary of the finding* regarding PC* In the three survey and turvtil* tone* program* are Uated in Table Although th* data are ineom* plot*, it la evident from (hit table that PCBe continue to contaminate our food. .Results of th* FDA Pesticide Survaillence Program appear to indicate an Increaea in the extent of contamina* tion, while those of th* usoa Surveil* lane* Program Indicate a decrease: this apparent conflict may ba explained by the fact that different foods are sampled in theae programs, and it is quite possible that contamination of some kinds of foods has decreased while It hes increeeed In others. The apparent decreaae in cho levels of PCBs reported in the pda Total Met Program Survty between fiscal year 1973 and the first half of fiscal year 1974 must ba viewed with cau* tion. During tha first half of fiscal year 1974, tha averaga PCi levels for mUfc and other dairy product!, for cgft and cm products, and for animal feed in* pedients ware equal to or greater than those reported for fiscal year 1973. ecu am bat** eaneveue v tiw pda PmuWOS Survtmanee Preeram face Hmm twa n vm im nhhmii i* eeier* mm* toe amount* at pea* m ** e anaenanai aee*aia**e i**ei. Environment, vw. 1 a. No. < TABLE 1 COMPILATION OF DATA PROM FEDERAL SOURCES FDA Pesticide Surveillance Program Year Numeer ef Sample* Peraont Centcmlnatee 15,000 3.2 Fiscal 1973 Fiscal 1974 7.882 1.723 4.0 5.4 FDA Total Diet Program Survey Numear el Cemeetlto Year ** Samela* PereeM CenlaiMnata# 1968*71 Fiscal 1973 Fiseal 1974 900 360 360 6 6 4 USDA Surveltlanca Program Year Mumeer *t iimpn Ptreeni CMtanMnate* 1971 Fiscal 1973 (Poultry only) Fiscal 1974 (Poultry only) 4.175 1,037 574 4.0 2.6 1.0 Level* ef Contamination "detectable" (fish, specifically! 1-10 ppm) "detectable" "detectable" Level* ef Smumnum trace -- 0.36 ppm trace-6.0 ppm trace -- 0.05 ppm L*v*H er Contamination trace -- 15 ppm trace -- 4 ppm 1.25 ppm Than why la there an apparent de* crease between >973 and 1974? in large part, this reflects an apparent de* crease in the number of fish that were found to be contaminated with pcbs. In fiscal year 1973. 62.2 percent of tha fish aaniplea examined contained PCBa ranging from trace amounts to 123 ppm. In th* first half of fiscal year 1974, only 35.3 percent of the samples checked were contaminated, and the leveia found ranged from trace amounts to 9.7 ppm. However, the fish data reported for fiscal year 1973 in cluded mostly freshwater fish, in which pc a contamination has been shown to be greatest, while during the first halt of fiscal year 1974 the samples con sisted mainly of marine fish. Since the samples are not comparable, the apparent decrease is probably a reflec tion of the difference in levels of pcu contamination between freshwater ami marine fish rather than an indication 13 moms 0B739B of i general decline in PCBs in fish. In addition to these observations, numerous specific incidents of pcb contamination of food have been re ported by the fda and the usda. In 1970, the Campbell Soup Company de lected high levels of PC ns (26.8 ppm on a fat basis) in chickens grown in .New York state. As s result. 140,450 chickens were destroyed. In July 197). the Monsanto Company informed the fua that large amounts of fish meal might have been contaminated with PC us during the pasteurisation process, due to a leak m the heating system at the company's East Coast Terminal in Wilmington, North Carolina. An Investigution by the FDA revealed that the leak had begun in April 1971 and had continued through July 1971. Contam ination of the fish meal was verified, snd, as a result, over 123,000 pounds of egg products and 88,000 chickens were destroyed. That same year, the FDA wet notified that high levals of PCBs 120 ppm) had been found in Swift and Company turkeys. As a re sult, approximately 1,000,000 birds were kept from market.1 These inci dents end the results of the federal sur veillance programs demonstrate further that contamination of food by reps is not s new phenomenon; it is a con tinuing problem which haa resulted in part from the continued indiscriminate discharge of PCB* into the environ ment, end it is one which must be eliminated because of the severe health haturds posed by these compounds. "Acceptable Dietary Intake" The FDA has calculated what is termed an "scceptable daily dietary in take" (ot pc as in the human diet - or a level of PC is which, if ingested for an extended period of time, would be loxicologically insignificant. Even if the validity of such a concept is as sumed, the basis for establishing such a level must be evaluated.'In this connec tion, the FDA's final environmental impact statement for ralemaking on fobs* indicated that both animal and human toxicological data were used to establish en allowable dietary intake for human beings. According to data {hen available (1973), long-term studies of dogs and rats showed "no-effect levels" (the dose levels below which the effects looked for were not observed) of 10 ppm for three commercial types of PCBs (Aroclors 1242. 1254, and 1260) fed In the diet. Employing the stan dard 1,00-to-1 safety factor used in applying results of animal experiments to human health standards, a no-effect level for human beings, based on data derived from the dog experiments, was 14 tt appears that the metab. ofism and excretion of PCBs, especially of Aroclors with high chlorine content, are even slower than for some of the most persistent pesticides, such as dieldrin and DDT. calculated to be an intake of 0.0025 milligram per kiioiram of body weight per day. From the data on rats, t fig ure of 0.003 milligram per kilogram of body weight was obtained. On the basis of the tests in dogs, the allowable level of PC B intake in a man weighing 70 kilograms (about 155 pounds) was figured to be 0.175 milligram per day (70 kilograms x 0.0025 milligram). The human toxicological data used in determining the allowable daily dose were derived from investigations of human PCB poisonings in Japan. In 1968. over 1.000 Japanese persons ex perienced PCB poisoning after consum ing rice oil contaminated with Kanechlor 40Q.''*10 In addition to causing headaches, swelling of eyelids, tempor ary loss of vision, and many other symptoms, PCBs stored in the adipose tissue (connective tissue containing stored cellular tat) of pregnant women were passed through the placental wall to the fetuses. As a result, nine of the ten live-born babies had unusually greyish, darkened skin, snd most were born underweight. The outbreak was interpreted by the FDa to haw the following implica tions for pcb intake standards:* "Since 2.000 milligrams was re ported to be the average total dose causing an effect in the Japanese, it is possible that 200 milligrams total dot age PCBs (applying a safety factor of 10 to I) may be tolerated over a much more protracted period of time with out overt adverse effect if daUy expos ure is held to minimal levels. This would permit ingestion of 4 micro grains 10.004 milligraml per kilogram body weight per day in a 70-kilogram man. Since the lowest total dose pro ducing an effect in man in the Japa nese incident was 500 milligrams, e similar analysis leads to an allowable protracted ingestion of I microgram 10.001 milligram) pet kilogram body weight per day s derived from a 70kilogram man." On the basis of these data, the kda arrived at an allowable dose of PCBs (for a 70-kilogram man) of 70 to 280 micrograms per day - or 0.07 to 0.2t milligram per day - compared to the 0.(7 5 milligram-per-day permtsable level established on the basis of the dog experiments. The validity of these calculations is very questionable, how ever. Particularly suspect are the ntimetes that had to be made of doaes received by individual Japanese, as veil as the erbitrsry assumption that s safety (actor of 10 to I is sufficient to determine i safe level of intake for "protracted period of time." in iMh tion, the calculations fail to consider the potential long-term effects caused by stored pcb residues. Furthermore, according to H. Mumenthal (acting director, Division of Toxicology, Bureau of Foods, FDA) in the time since these calculations were made, there have been two impellent experimental observations nrnnrtdog pees which make the previously celenlated allowable daily intake level oheo lets:2 First, racent studies by J. K. Alien end his colletfues on tht effects of low-level exposure of nonhumea pit mates to PCBs must be consAdered.'i"1*1* Tht efftcli wtn la these studies of monkeys are similes in appearance snd persistence to the symptoms of the human poisoning Ise Japan. Moreover, these symptoms wees documented at dietary intake levels as low s 2.5 ppm (equivalent to about 2.5 milligrams per kilogram of body weight). To date, a no-efract level for PCBs in monkeys has not been estab lished. This would indicate that dose end rets ire not particularly reliable subjects for tests relating to primatea, since they are not ee sensitive as are primatea to many of the toxic effects of PCBS. Second, Allen's work indicates that the uss of grots observations of 1 oxic ily are not reliable in the study of PCBs.11 Allen observed that routine toxicological evaluations of rati wMch were fed 100 ppm Aroclor 1248 for one year revealed no abnormalities ui growth, mortality, or hematology. However, more sophisticated testa showed that these rats experienced drastically altered fat and cholesterol metabolism as well at changes in liver sice and structure. Therefore, even If an allowable human daily dosage for fees calculated from animal toxicolog ical data ware acceptable, the basis for the nwt 1972 calculation* would be seriously questionable. Th chemical nature of rt`Ds mny help (o explain in part wby they are tubaeuwly and chronically toxic. The March UTS MQNS 087393 chemicals have a low solubility in water hut are highly soluble in fat;1* thvrefore, they tend to accumulate and . concentrate in the body's fat stores rather than being rapidly metabolized and excreted. It appears that the me* tabolism and excretion of PC os. espe* dally of Arectors with high chlorine content, are even slower then for some of the most persistent pesticides, such as dieldrin and t> i> V. * * Thus, after in* gestion, pens persist in the body for long periods of time snd may thereby elicil chronic effects. Exeesaive Intake Is Common The pda'i acceptable daily pcb intake level of 75 to 210 micrograms per day for a 70-kilogram man seems debatable at best, As i. Weasel, scientific coor* dinator of the foa, has pointed out,1 "It is quite clear that the acceptable daily rep intake of 75*210 inlcrograms per day could easily be exceeded by an adult consuming some of the heavily contaminated foods in hit diet." Table 2, taken directly from Weeael's testi mony,1 illustrates this point clearly: Consuming i steady diet of combined foods from the Hit would produce con* detent over-exposure to pets if each food had the maximum allowed con* eantrition of pcbi (listed under the heading "Temporary Tolerance Ippral"). At WaaMl conclude*, "Even when PCia are present at the (permissible) tolerance level, it would be possible for en adult, with normal dietary habits, to exceed 175 micrograms (0.17S mil* Igraml of pcbi per diy." Further more, adults with "normal dietary habits" ate not the only people who are vulnerable. Perhaps at even greater risk ire those large groups within the populellon (such as sport fishermen or people who require special diets) who consume aboveiverage quintittea of PCB*eontaminated foods, or nursing babies who ingtat rets in their mothers' comaminatad milk and who, for natural bioehamkal reasons, have a very limited capacity for metabolising foreign substances such at Pegs. A. Kotbye, Jr, associate director for science, Bureau of Foods, pda, snd H. Blumenthal are clearly conact when they say, respectively:1 T,> "Infants or young children could also readily exceed the tolerable daily exposure," snd, "Thus, the best evi* dance indicates that children would be more susceptible to the poisoning caused by unmetsboUsed re Be, since TABLE 3 relative contribution to acceptable daily intake (I7S mjet/t) BY POODS SUBJECT TO PCB TEMPORARY TOLERANCES Tyw ! r**a Serving ( Feel Temperery Tolerance (em) lamvetem Amount pees in Fee* notation COMrlNtlw t AOt Milk Cheese Poultry Egn Fish Packaged Food 800 ml (3.5 cups) 100 g (3.5 oz> ZOO 9 (7 oz) 100 g (2 eggs) 200 9 (7 or) 100-200 q (3.5-7.0 or) 2.5 (fat basis) 0.1 (whole product) 2.5 (fat basis) 0.6 (whole basis, assuming 25% fat) 5.0 (fat basis) 0.5 (whole basis, assuming 10% fat) O.S 60 meg 60 meg 100 meg 50 meg 5.0 1,000 meg 10.0 (Packaging) 10-60 meg* 46% 35% 58% 29% 580% 6-35% *Based on 1971 foa Survey that 10 ppm Fees in packaging can result in migra tion of 0.1 0*6 ppm aces to packaged food. see eeuoMne < iui ii *mhim m t tea. (AViMNMIWnt, v. tl, Ne. i MO NS 08 7394 15 ** twe tr*H foot mMpai mete* of photographs end lead-in excerpts, photo captions. end preparatioi of most graph* end illuuwioits which appear in Environment articles. .they have not developed effective ways of eiiminetins them from the body." Need for Roovtiuntlon The FDA's temporary tolerincei for PCBI in food are both inadequate and inappropriate; the acceptable daily done calculated in 1972 it now obeo* lete In light of more recent findings. More importantly, however, the appro* prietenees of an)1 "acceptable daily dote" for pcbs it highly questionable in light of new evidence demonstrating the carcinogenicity of them com* pounds in experimentel animals.1* Since there ie at preaent no adentitle evidence that any level of intake of a Tha USDA Survaillanca Program consists of pariodic sampling and analysis of maats and poultry for chamical con taminants, including PCBs. is carcinogen ie safe, the entire concept of an acceptable daily doee for carcino genic substances such as pc vs is con* trodktory and scientifically unsujK portable. Our growing concern about the con tinued contamination of food supplies by peas reflects an ever*incruising awareness of the extreme health hat* aids posed by these compounds. Fed eral sampling and surveillance programs have continually demonstrated the presence of pcbs in our food supply, and the existing temporary tolerance levels for PCBs established by the FDA have been insufficient to protect Che public health. A new regulatory pos ture is needed which takes into sc* count recent evidence of chronic ef fects caused by low-level dietary in takes of pcbs and. even more impor tantly, the new evidence substantiating the carcinogenicity of these com pounds in laboratory animals.1* Q The title of this erticle as originally submitted was "PCMs In Foods: A Look at Federal Government Respon sibilities. '* The Publisher and Editors of Environment ere responsible for the published titles end subtitles, selection NOTES >. Weaaw, j.A.. testimony on "PCdt in P*oor Pooe Packs*m Matafiau." Food ene (hat Amm.. watnmyton, o.C. {awaiaoia from Haarln* clarH's Oinca. ohm No. 79N.0OIJ). 2. Btumontnsi. m,, teeiimony on "pcbs lit Mow Com Oactoymy MalariaM." Pooo ane Drug Aomin., wsfninyton. O.C. laxlladla from Myartny Clerk'* Office. Ooeisot PM* 7SN.0013). I. Voitn, a.. "de**lina Concentration* of aMoteiyncieftelonrlnPeitsore*. 1*O7f1te.nyl Mana#t. OMOoTo.in fLoeodt*, *21, 1*78. 4. Hanlay, ft.. "*CB in Fl*n Mira Now State stuay,'' New rorti Timee, Som. ie, 1*78, S. Unko, A.A., * at.. "Occorranea of DOT ane PCS Compounds In asNIe Herrin* and Pika from m* Turku ArcMpaioeo," (jndr. non.. Tiies, i#74. S. unko, H.n.. o. Hantamaw, mg k. ij-qq. "PCS naaicwei in Plankton and Sadtmat M iho SouthwHltrn Coaat of PlnlCdd,'* tad. Imtr. CaMam. Toaloo*., 12)738, 1*74. 7. Cornotluaa4n, P.B., Iwiimony on "Pegs In moor Pooe Pacnoftne Malaria*," Pone and Orus Admin., WaaiMnyton. OX. lauadadM from Hsrn| Clark's Office, Oockat No. 7sn-ooi3). a. Food inf Drug Admin., larPMUMt to ins Pinal Cndrowmawm impaat Italamanfi MufamaMn* an Poryaniorinatad OfnaiifN. 197S, p. 7. . Hureuune, M.. "toidwnioioylc Study on Vwho. a Pafsonm* Causod ay diet Oil Cam temineto* wttn a commorefal Orand of POM* enterinatod Wphenyl*," Cnatr. Haatt* Mm Oddi., lillt. 1072. 10. Kurettune, M., **An AOMract of Aadd* of Laooratory CaenwneNont of Pationta HH Vuano and of Animal Kaesrimonta.1* CeaSr. HaaMk. MnpdW.. lillt. 1971. 11. Allan, J.H., "WaMonaa of Mo *fantiumon (Himat* t* Pa>hrcMom#tad Wanany) Know* aura." PtodraiMH Haase01ay*. MilSN, 1978. It. Allan, J.A.. i_A. Cdiim, and O.A, dor* aotti, "Pawoual tffasta of Sdorl.Term, Loan Laval (Rpoaura of Nonnuman primataa to Poiycniorlnaidd Oiononyla,'* TpMaot. and Am*. PharmadOt.. MiMS, 1974. 13. aertotti, O.A., and J.P. aina. "crtaci* of Poiycniortnaiad dsynanyi* on daaiadwa lion in tna Primal*," PtdaraMon Nodood* In**. J4i3Sa, 197S. 14. oartoaii. O.A.. P.j. Manar. and 1.4. Allan, "Adorodwctlv* Dysfunction* m ISO** aua Monk*** tapoaad to Low Lew* of Potycnlortnaiod Olon*nyli (Arooior 1249),'' p**e and Co*. Towsoi., m era**. is. AM*n. j.n., D.H. t4*roe*k, ane i.c. Haw, "Tiwud Modification in Monkoy* aa Snpos to Adsorption, CNMrldulion, and CacratMn of Poivcmormaiad tenony*," mad. eWr. cams**. towoo,, 2iee. itr*. ie. Kim*roun, n.a, MT*o ToMWty of Poivctuorinaiod Mlvcycn* Compound* and M(*t*d Cnamtcs*." CUB CrtUaa* dadaw* M t*m*i,, jan. 1*74, p. aas. 17. Ko**vd, A.C., Jr., tastimony pn "PCBa In PdPdf Pood Packs*ia* Maiort*u.'' Food end Oru* Admin.. MewNnyton. O.C. l--ailddN from Maarme CiarM't Offldd. DMM No, 79N-04I3). IS. Kimeroun, 4,0., at at.. ``Induction of Uvor Tumor* in Snorman SIram FamoN Aal* ov Poiycmormalpd dipk*nyf ArodMr 1290," Clr. for Oimm* Contrn Aiiania, Ok, in drddl. Marcn 1979 HONS 087395 v-> IN CASE OF LEAK OR SPILL, CALL COLLECT 618 271-5835 This product contains POLYCHLORI NATED BIPHENYLS (PCB's) which seme studies have shown may be per sistent, an environmental contaminant and. possibly, injurious to certain forms of bird, aquatic and animal life. PREVENT ANY ENTRY INTO THE ENVI RONMENT THROUGH SPILLS. LEAK AGE. DISPOSAL, VAPOURISATION, RE USE OF CONTAINERS OR OTHERWISE. SPILLS, LEAKAGES AND WASTE PROD UCT MUST BE COLLECTED. Use of this product must be restricted to applications which can be controlled so that entry into the environment does not occur and to applications in which it cannot come into contact with food, animal feedstuffs or pharmaceuticals. HARMFUL SUBSTANCE IF TAKEN IN TERNALLY OR IF IN PROLONGED CONTACT WITH THE SKIN. CAUSES IRRITATION OF SKIN AND EYE$. DURING SHIPMENT AVOID SPILLS AND LEAKAGE INTO INLAND WATERWAYS AND THE SEA. WASTE DISPOSAL With prior Monsanto notilication used polychlori nated biphenyl fluids may be returned freight pre paid for proper incineration at 3< per pound. CAUTION! CONTAINS CHLORINATED HYDROCARBONS Store away from food, animal feedstuffs and pharmaceuticals. Keep container tightly closed. Do not eat or smoke when using. Avoid breathing vapours, mist or fumes. Do not wear contaminated clothing. Wash product from skin with soap and water. Wash eyes by flushing with water. Ship to: Supervisor Dept. 831 MONSANTO COMPANY SAUGET, ILLINOIS 62201 LABEL ATTACHED ON ENDS AND SIDES OF TANK CARS 1249/53 HONS 087396