Document 44jJRynRVn3p8p0bZeRdr3xVp

0 - /^i 9 m 'f Polychlorinated Biphenyls Another Long-Life Widespread Chemical in the Environment David B. Peakall and Jeffrey L. Lincer The recent finding that pelagic birds dying on (he coasts of Great Britian had polychlorinated biphenyls (PCBs) in (heir livers in concentrations of several hun dred parts per million (Bourne and Mead, 1969) shows that these compounds are present in the ecosystem in large amounts. Thus, it seems worthwhile to summarize and evaluate our current knowledge of these compounds. Structural and Physical Properties The picture is complicated by the fact that we are not dealing with a single com pound. The basic structure of PCBs is shown in Figure I. Any of the positions marked with an x can be substituted by chlorine. Widmark (1968) has calculated that of the 210 possible combinations 102 are probable. His criteria for these lim itations are those compounds containing five to eight chlorine atoms per molecule and the number of chlorine atoms per ring differing by not more than one. The commercially available Arodors (Monsanto Company Trademark) are des ignated by numbers (Monsanto Technical Bulletins). The first two digits represent the molecular type: 12 chlorinated bi phenyls; 25 and 44 blends of chlorinated biphenyls and chlorinated terphenyls (75% biphenyl and 60% biphenyl, re spectively): 54 chlorinated terphenyls. The last two digits give the weight per cent of chlorine. Thus, Aroclor 1242 is a chlorinated biphenyl containing 42% chlo rine. The biphenyls commercially avail able from Monsanto range from 21% to 68% chlorine. Mass spectrographic studies of Aroclor 1260 (Koeman et a!., 1969a) show the presence of 11 isomers: five con taining six chlorine atoms, five containing seven chlorine atoms, and one containing eight. Bagley et al. (1970), studying Arodor 1254, found 18 compounds: one con taining three chlorine alum*, four contain ing four chlorines, four containing five chlorines, five containing six chlorines, and four containing seven chlorines. Thus, T>> ,* m iht L|mu*r Lbriory, Comat UWmnii)', IlhoM, N Y, the number of compounds present is, for tunately, much smaller than is theoretical ly possible. PCBs are chemically inert, are not hy drolyzed by water, and resist alkalies, acids, and corrosive chemicals. They have low volatility, their boiling points ranging from 278 C for Aroclor 1221 to'415 C for Aroclor 1268 (Penning, 1930). All are stable to prolonged heating at 150 C. and the lower Arodors can be distilled at atmospheric pressure without appreciable decomposition. PCBs are described as in soluble in water and very soluble in hydro carbon solvents, although no exact figures appear to be available. Nothing is known about the biological decomposition of PCBs, but it is likely that they are more stable than DDT and its metabolites since they lack the ethane component between the aromatic rings, which is the site of attion of most of the transformations of DDT. Thus, PCBs have''the necessary physical and chemical characteristics for persistence and accumulation up the food chain. Use of PCBs Polychlorinated biphenyls were first de scribed in the literature in 1881 (Schmidt and Shultz, 188th and the successful com mercial production was achieved by the Swann Company in 1930. fn that year the physical characteristics and commerical possibilities of these materials was de scribed by Penning (1930). PCBs are now manufactured by Monsanto in the United States (Trade name Aroclor), Prodel6e in France (Phenochlor), and Bayer in Ger many (Colphen). Other manufacturers are located in Japan and the Soviet Union. No figures of the amount of these mate rials produced annually are available, but to judge from the uses listed in Table I they may be very large. The uses listed in the table are only suggested applications taken from Technical Bulletin 306 of the Monsanto Chemical Company, and again there is no information on the extent to which these recommendations are acted upon by the manufacturers of plastics and resins. The use of highly chlorinated Aroclors for extending the kill-life of formulations containing chlordane.,aldrin, and dieidrin arc mentioned under miscellaneous appli cations of Aroclors. This possibility has been considered in a number of papers. Sullivan and Hornsiein (1953), Hornstein and Sullivan (1953), and Tsao et al. (1953) found that the chlorinated terphenyf Aro clor 5460 increased the residual persis tence of lindane. Tsao et al. (1953) consid ered that there was some indication that chlorinated polyphenyl may have a syner gistic effect with lindane. Duda (1957) ____) m____ % OO XXX X x msutti mem roa suuamunoN or chlomni <A> OiO o -to MONS 087211 OO OKMLOKXMMOm. I. Bask structure o( PCtts (Al and possible rtscikm at PCBs (lit. sprayed dm saplings with a lindane Aroclor 3460 mixture (1:4) and then tested the residual effect on the leaves to infes tation with dm leaf beetle (Caltrucella xanthomelatnn). He found tbut leaves treated with lindane plus Arodor were protected longer and that the insecticidal effect was more rapid than with lindane lone. Peaks corresponding to Arodor $460 have not been detected in the envi ronment. However, under conditions of temperuture and now-rate commonly used for gas chromatographic analysis these compounds would not be detected (Reyn olds, 1970). Nearly 2$ years ago it wus noted that Arodor 1242 was one of 17$ compounds out of 6000 tested that was effective against mosquito (Aegyps) larvae (Deonier et at., 1946). Lichtenstein et at. (1969) tested the effect of adding a variety of biphenyls and terphenyls to DOT and dieldrin with respect to their toxicity to house and fruit flies. It was found that PCBi had very low toxicity to house flies when given alone but PCBs increased the toxicity of dieldrin und DDT. especially the letter. The effectiveness of these com pounds decreased as the chlorinated level increased. For example. Aroclor 1211 in creased the mortality of fruit flies from $9% to 93%, whereas Aroclor 1268 in creased it to only 77%. Analytical Methods I) Meniljlcaiion. Since various com pounds with electron-capturing properties have been tentatively identified in atmo, spheric samples in the pus! (Abbott et ai., 1966), and some pesticides are capable of hybridizing in the soil to form a new com pound (Bortha, 1969), it is important that the presence of PCBs in field samples be proven beyond doubt. Identification by means of a combination of high resolution gat chromatography and mass spectrom etry has been carried out by three inde pendent laboratories in Sweden (Widmark, 1967), Holland (Koemun et al., I969e), and the United States (Bagley et al., 1970). Widmnrk's report states that all peaks were identified by mass spectrom etry (although no duta were given), but Kocman and co-workers gave full experi mental details, and Bagley et ul. (l70) demonstrated that most chemicals in the eagle samples examined were components of Aroclor 1254. Thus, despite a recent statement by the Monsanto Chemical Company (in Risebrough. 1970) that the case for labeling the peaks in question as PCBs was not proven, there is enough evidence to convince an unbaised scienti fic jury. 2) Separation. The chemical techniques preliminary to quantitation of residues in samples containing both PCBs and chlo rinated hydrocarbon pesticides fall into two groups--those necessitating the de struction or alteration of one or mote of the compounds, and those which do not. Included in the first group is nitration. Treatment with a 1:1 mixture of sulfuric acid nitric acid at 0 C for 5 min destroys or alters aldrin, p.p'-DDE, p.p'-DDD (TDE), p.p'-DDT, and dieldrin such that they can no longer be detected at the original position on the chromatogram. This procedure leaves unaffected PCB, lindane, and BHC (Jensen and Widmark. 1967). A more rigorous nitration with a 1:1 mixture of sulfuric acid-fuming nitric acid for 15 min at room temperature re moves. in addition to DDT and its related products, nidrin, hepiachlor, Kelthune, Perthane, Tedion, Telodrin, and Trithion while lindunc, hepiachlor epoxide, toxaphene, and Strobane are not removed (Erro et al., 1967). Risebrough et al. (1969) reported that this nitration also removed the chromatographic peaks of PCBs. Rey nolds (1969) reported that his attempts to nitrate samples were not fully successful in that there appeared to be loss of some of (he more volatile PCBs while peaks with longer retention times appeared. Armour and Burke (1969) reported that complex chromatograms resulted after nitration which could not be related to the unreacted DDT-PC8 mixture, and nitra tion was not pursued as a practical means of separating DOT and PCB for further tests. Saponification with alcoholic NaOH or KOH will dchyrodrochlorinate Perthane, Toxaphene, DDD, and DDT to their re spective olefins (Archer and Crosby. 1966; Klein and Watts. 1964). Risebrough ei at. (1969) reported that PCB peaks are not removed or displaced but gave no duta. The second, and in some instances more desirable, group of analytical tech niques allows the special separation of many chlorinated hydrocarbon pesticides from PCBs. Reynolds (1969, 1970) re ported on an activated Florisil column technique which separated heptachlor. aldrin, DDE, and PCB with the first elu tion (60 ml n-hexune) from lindune: hep tachlor epoxide, DDD. and DDT with the second elution (40 ml 50% ethyl ether in hexane). Armour and Burke (1970) devel oped a method utilizing a silicic acidCelite column eluting aldrin and PCB with the first fraction (250 ml petroleum ether), and lindane, heptachlor. hepta chlor epoxide, dieldrin, endrin, p.p'DDE. o.p'-DDT. p,p'-DDT, and p.p'DDD with the second fraction (200 ml acetonitrile hexane methylene chloride-- 1:19:80). Koeman et al. (1969a), using an activated Florisil column, eluted the apo lar compounds including DDE and PCB with hexane, und then dieldrin and endrin with 10% diethyl ether in hexane. Mulhern (1968) reported on a method which utilized silica gel-coated thin-layer plates September I. 1970 and hexane/ethyl ether <98.2) solvent system. The plates were developed, pprayed with a silver nitrate solution, and exposed to UV light. The plates were then divided into five horizontal sections. Dieldrin, endrin, 7-BHC, heptachlor epoxide, p,p'-DDD, p.p'-DDT, o,p'DDT, and p,p'*DDE (.in that order) were found in the first four fractions, while most of the interfering compounds found in wildlife samples were found in the fifth zone. Bagley et al. (1970) used this meth-od but mentioned that zones three and four contained practically all unknown components as well as p.p'-DDT (zone three) and p.p'-DDE (zone four). Armour and Burke (1969) used precoated (alu minum oxide) sheets and n-heptane and 2% acetone/n-heptane for solvent sys tems. PCBs (Arodors 1254 and 1260) and DDE were not separated, but p.p'-DDT and p,p'-DDD were completely sep arated from PCB by both solvent systems. Another possible means of separating in terfering substances is to use a series of differing polarity columns in the gas chro matograph at the lime of determination. This is less time consuming and may be useful when operating conditions can be selected such that PCB peaks are absent in the region where sought pesticides emerge (Simmons and Tatton, 1967). 3) Quantitation. Koeman et al. (1969a) semiquantitatively measured the residues in Japanese quail fed phenochlor DP6 by using one of the peaks in a phenochlor DP6 mixture as a standard. Risebrough (1969) quantitoted relative levels of PCBs by assuming that each PCB compound produced the same peak height with the electron capture detector as the same amount by weight of p.p'-DDE. After summing the heights of the individual peaks, the total was multiplied by a factor derived from measurements of standard solutions with electron capture and microcoulometric detectors. Jensen et al. (1969) reported PCB amounts as the sum of al! PCB components and based the estimate on a combination of mass spectrometry and microcoutometric and electron cap ture detection. Even with this elaborate approach, these investigators suggest that the method is stilt rough and ma; be cor rect only within a factor of 2. Anderson et al. (1969) devised a method for obtaining a crude estimate of PCB residues as Aroclor 1234 from chromatograms where sep aration had not been attempted. On an empirical basis, it was found that Aroclor 1254 could be quantitated by considering peak 10 as p.p'-DDT and multiplying that value by 10. Since this peak had originally been quantitated as p.p'-DDT, and in fact many of the original samples con tained little or no p.p'DDT, it was pos sible to estimate relative PCB values. Anderson and his co-workers also saponi fied samples to remove interfering p.p'DDT and p,p'-TDE and then quantitated PCBs as Aroclor 1254 by relating sample peaks 9 and 10 to the corresponding peaks of an Aroclor 1254 standard. Reynolds (1970) employed a method similar to Koeman et al. (1969a) but based his quan titation on an average of two or more peaks. In addition, his results were re ported as Aroclor 1254 or 1260 depending on the overall pattern of the chroma tographic peak profile. It is clear that we are still relatively unsophisticated in our PCB quantitation methodology and will continue to estimate only relative amounts of PCBs in field samples until we'synthe size the individual PCB components com monly found in the ecosystem and are able to speak in terms of these individual peaks as we do for most pesticide residues. However, it has been kindly pointed out (Risebrough, pets, comm.) that, with ref erence to biological significance, the cor rect order of magnitude and accurate rela tive amounts of PCB give the essential information. This is because biological effects, such as enzyme induction, are re lated to degree of chlorination, and the existing methods give some indication of this' activity. Therefore, thaMnformation would be lost if stress were placed only upon quantitating individual peaks. 4) Magnitude of Error. Ever since PCB peaks were recognized for what they are, residue chemists and other researchers interested in pesticide residues have asked what magnitude of error is likely to result from ignoring the presence of PCBs. Only recently have studies either directly or indirectly resulted in an esti mate of this error. Anderson et al. (1969) quantitated p.p'-DDE, p,p'-DDD, and p,p'-DDT in five egg samples before and after saponification. There was no appre ciable change in the p.p'-DDE, but ap parent p.p'-DDD was reduced by ap proximately 58% and p.p'-DDT by 90%. Reynolds (1970) looked at a large number of samples before and after his PCBFlorisil separation and found .hat the actual p.p'-DDD residue (relative to the apparent residue) represented from 0 to 7%,in California gulf (Lana occidentals) fat, 0% in cormorant (Phalacrocorax auriruj) eggs. 80% in 10 pooled mallard (Anas platyrhynchos) duck eggs, and Irom 0 to 104% in great blue heron (Ardea cinerea) eggs. Respective values for p.p'-DDT wereO to 53%, 13 to 41%, 100%, and 18 to 102%. Actual residue levels of heptachlor epoxide generally represented a majority of the apparent values. Before and after values for p.p'-DDE and dietdrin were not significantly different. Obviously, the magnitude of error may vary depending on the trophic level sampled and certainly with the area from which a sample is col lected (Risebrough et al., 1968, Jensen et ai., 1969). Since the publishing of ade quate separation techniques, there is no reason why there should be any error in pesticide quantitation contributed by PCBs. Toxicology Despite some recent studies, the toxi cology of PCBs remains rather poorly known as compared to that of the chlo rinated hydrocarbon pesticides. For ex ample. no definite work has been done to establish LD50 values for the various formulations of PCBs. 1) Acute, single dose experiments. Tucker and Crabtree (1970) found that a single dose of 100 mg/kg Aroclor 1234 (stomach tubed in oil) was fatal to two out o( three rats, while 500 mg/kg was not fatal to three rats. Aroclor 1268 killed one rat out of three at 500 mg/kg, 1000 mg/ kg. 2000 mg/kg, and 4000 mg/kg. Smyth (1931) found that a 4 g/kg (degree of chlo rination not stated) was nontoxic to guinea pigs and rabbits, but this appears to be due to the fact that materia) which was given as a paste passed through the intes tine unabsorbed. Tucker and Crabtree (1970) found that Aroclor 1242, 1254, 1260, and 1268 at a dose of 2000 mg/kg was not fatal to mallard ducks (four groups of three birds each). 2) Acute, feeding experiments. Mon santo Bulletin 306 states that 100 ppm diet had no effect on rats, although no details of the studies were given. The ex periments of Bennett et al, (1938) in which 0.05 g/rat of 65% chlorine biphenyl was given orally every other day ted to 50% mortality. If one assumes a body weight of 200 g, then the alternate day dose is roughly 250 mg/kg. which can be com pared to oral LDS0 for DDT of 113 mg/Kg (Frear. 1968). Miller (1944) found that two oral doses of 69 mg of 42% chlorine biphenyl a week apart were fatal to guinea pigs. At an estimated body weight of 400 g, this gives a dose of 170 mg/kg. Tucker and Crabtree (1970) fed rats diets contain ing 10 and 1000 ppm Aroclor 1254. One rat out of six on the low dose died; this mortality was considered to be due to other causes. Four out of four of the high group died within 53 days and the cal culated intake was 1330-1520 mg/kg. The MOWS 0 0 7 2 1 3 960 food intake of the 1000 ppm group was only 79& of the control group. Picul cl ai. (1970) have examined the tokicity of Aroclor 1254 to Bengalese finches {Lonchura striata). This is a diffi cult species for which lo calculate the dietary intake. Due to their dependence upon unshelled food, it is only possible to present the PCB-lodcn food for a few hours a day (Jefferies, 1967). Loss by evaporation and loss by spillage must be allowed for, and increase of weight by def ecation must be kept to a minimum. Thus, the calculated dietary intake is sub ject to more error than is usually (he case. Prcast et al. (1970) also measured the con centration of PCBs in the liver; they found that the range was large (i.e., 70 697 ppm in birds that died compured to 3-634 ppm in those that survived). These authors conclude that Aroclor 1254 has only 1/13 the toxicity of DDT, although the different shape of the mortality curves--steep with DDT, gradual with PCB--makes comparison difficult. Jef feries and Walker (1966) found good cor relation between calculated dietary intake and liver concentrations for pp'-DDT in the Bengalese . finch. However, other workers (Dale et al., 1963; Stickel et al.. 1966; Stickel and Stickel, 1969) have con sidered that levels in the brain are a more reliable index of toxic levels than those in the liver or whole carcass. De Vos and Koeman (1970) fed Phenocfor DP6, Clophen A60, and Aroclor 1260 to chickens et a dosage of 400 ppm. Mor tality was complete (20/20) for those birds on Phenoctor in 12-38 days and in 13-29 days for Clophen. The mortality for Aro clor was only 3/20 for a 60-day period. This differential effect is unexplained and is surprising In view of the fact that all three formulations contain 60% chlorine. These workers measured the residue lev els in the liver, and, for some birds, in the brain, for chickens dying during the ex periment. Although there was consider able variation, most of the brain levels were between 210 and 420 ppm, which can be compared to 30-80 ppm for DDT (Stickel et al., 1966). On the basis of this work, PCB is 1/4-1/5 as toxic as DDT. Little difference was noted between the three different PCB formulations, al though the numbers of determinations involved was rather small, if this finding fs borne out by subsequent work, it would suggest that differential absorption from tba gut or differential penetration of the blood brain barrier is involved. The liver values were more variable. There was a considerable number in the 200-400 ppm range, but there were several values in excess of 2000 ppm; This finding is in agreement with the findings of Dale, Stickel, and co-workers that the brain levels are the best indication of acute loxic levels. McCune et al. (1962) found no mor tality with chickens fed 100 or 200 ppm Aroclor 1242 in their diet for a 4-week period. On diets of 400 ppm and 800 ppm, the mortalities over a 4-week period were, respectively, 50% and 90%. During the first 3 weeks, the mortality figures were 10% and 50%, respectively. Flick et al. (1965), using the same material at 400 ppm in the diet, had three birds out of 24 die in a 3-week period. Koeman cl al. (1969a) found that a diet containing 2000 ppm Phenoclor DP6 caused complete mortality with Japanese quail (5/5) in 5IJ days and rats (8/8) in 1-56 days. Schoeltger (unpublished) found that the 96-hr TLm for Aroclor 1221 using cut throat trout was 1.2 mg/I and for Aroclor 1260 was 60.9 mg/1. In general, they found that the toxicity o( Aroclors was inversely proportional to their percentage chlorination and directly proportional to their solubilities. These figures suggest that PCBs ^re.two to three orders of mag nitude las toxic to fish than DDT. \{/ork by Lichtenstein et al. (1969) on house and fruit flies found that PCBs were 40-300 limes less toxic than DDT. the toxicity decreasing as the chlorine content in creases. Thus, it appears that the lower vertebrates and invertebrates are much tess susceptible than mammals to direct toxicity from PCBs. 3) Sublethal effects. As with the chlo rinated hydrocarbon pesticides, the most important effects are long-range sublethal effects. The pathologic changes in various organs are summarized in Table 2. The table.shows some interesting differences between mammals and birds. The most striking finds in mammals arc alterations to the liver, whereas fluid in the peri cardial sac, kidney damage, and reduced spleen was found in birds. McLaughlin et at. (1963) found that 25 mg Aroclor 1242 injected into the yolk sac of chicken eggs caused complete mor' taliiy, whereas 10 mg caused 95% failure and (eratogenetic effects were noted among the young that hatched (beak deformity, edema, and growth retardant). Induction of hepatie hydroxylating en zymes has been demonstrated in the pi geon (Risebrough et al., 1968), rat (Street et al., 1969), and American kestrel (Falco sparverius) (Lincer and Peakall, 1970). Street and co-workers studied the effects of a diet of 50 ppm and 100 ppm on sleep ing time induced by a standard dose of hexobarbital, in vitro rates of aniline hydroxylalion and dcmethylation of p-nitro- anrsofe, and the rate of excretion of dieldrim These workers studied 10 com pounds ranging in chlorine content from 21% to 68% and found that all the effects increased with increasing chlorine con tent. For example, 50 ppm of Aroclor 1221 reduced hexobarbital sleeping time by IJ%, whereas for Aroclor 1248 and 1268 the figures were, respectively, 35% and 48%. Thus, the sublethal effects have direct correlation with chlorine content, while the lethal effects appear to be in versely correlated (Tucker and Crabtree, in press). Lincer and Peakall (1970) noted an increase of the in vitro rate of metabo lism of estradiol in kestrels fed 0.5 and 5 ppm Aroclor 1254 in their diet and also demonstrated increased levels of cytoplas mic RNA with the higher dietary level using a cytophotometric technique. Tucker (unpublished) found that a sin gle oral dose of 500 mg/kg Aroclor 1254 caused regular egg laying of Japanese quail (Coiurnix coturnix) to turn first to scattered egg production and then to stop completely for a week. The scattered eggs had shells 9% thinner than normal, but thickness returned to control values when regular laying was resumed. Mallard ducks dosed with 1000 mg/kg of Aroclor laid one or no eggs before stopping for I2 weeks. The few eggs laid after the sin gle large dose of Aroclor had shells 18% thinner, and again eggshell thickness was normal after resumption of regular laying. The period before ejg laying has been noted (o be increased in the ring dove (Peakall. unpublished). It is possible that the mechanism involved is increased rate of metabolism of circulating estradiol in the liver (Peakall. 1970). Anderson et al. (1969) had suggestive evidence that PCBs affected eggshell thickness, al though to a less extent than DDE. Pre liminary results with ring doves support this conclusion (Peakall, unpublished). Levels of PCBs Found in Nature Roburn (1965), comparing total chlorine (by concentration cell techniques) with results calculated from gas chromatog raphy, found that some unknown chlorine compounds were present in seveul tissue samples and eggs of wild birds in Great Britain. The first identification of these materials was by Jensen and it is stated (Anonymous. 1966) that residues in feath ers collected in Sweden go back to 1944. PCB residues have been reported in wild life from Canada (Holden and Marsden. 1967; ` et al., 1969; Reynolds. September t, 1970 MGNS 0872X4 961 TAME 2. Paltiatapic chauf*s tadaca4 fey PCI* Tmatua* ShtfU*M iit(itno 2Ma*d*y<w MBS** ft* aptplmatba mm Mu* Mai a* Bat tkw> HSaar SmS fit *tflm tfcr--* MUn, **|M m mStull inHfU itrapBr. Ik* amaUt aatad la a In* MlMtft. EaaaatlaSy aam* tut! awaSaa. SyUtM pandit ptNUi MM dM will* fiw *r*. Mm|H 122% waigfet iatrin*. twtf uMm ft feyaRat ytMN biytiflMi Snwttiad PaiiaatMa tad Mftntaa OHw OkimtUt thaaeaa N* aatawaitby cfcaaft* Admail, ifltM. nd paatraat *wU aa Mtawarthy efcaafUk litwan Mw it1441 laaaatt M M. 1192* Iwwatt fS.IM1M toOMtMlS **<11.11% Cl AwUwt) Rat 199 spa la * 299ppaladtol eetppatoun Hi ppwiadta mil CMrtn IHMMwi CNaMu bMlMl waaka |4l)UUicM VWtMM *4M 4Q.A<wM lt*|UM ffewfe HI m k M tar N ** imai Odabaa Imiuh la waigbt. pfftM UtiaaiMf wNfe btrMiit| OdartM tmtlM. fti*t*i 1212-19%. 1142.12%, tzss14%, 1211-24% it IS pp*. Soph MU.Ua praaM Ntpffact NiMflM Uh|U pad Mfltad P--|Ul ihtunw mu unit ** Myditptrtea*dhMi Hydiapaffcar*m NyStayaikaHa* feydtpparilntm Mm* Nam at 209 ppn. artaattva feiwpwfepll, pad aMirstiaaat at 4N na. larratsad Bad la panaMW ntattha MybwtnaaatiaUaa. mmwwmu. man '; MtMHafpaacfppa.au> tH--wt tf pdmU aad twal apiaa at law caata* ttaMw. Al Mgkat aaatwu Intiaaa pdt niia wlaiU paawan. adrcaah MMnSapa. fMlMditHS) Hi wMs* cfcunif Wwfbtwn 22.4% af Mala *wUyhttn faatfUaaaS 13.1% Ilf tfeMP dyiaf baa VC> pahiaws. INsSt wM|bt hernia, aftwihtwadRfMd * irfpaikwUU ml BrapM at ai Itw pnnt . CmmMUw MtiiUa (w*H 1 nd It. li*w wU|M WmiH (tan 2.71 ffM9 |ta 4.21 |/199 pfrpwpa S). fatty *|w> awUaai Tafeatar HataHaa, (nm* 1 nd 21 Bara witfe ua>t 3. Hydraparicariwa MiMM with ewapda. 1 a*d2. ftatawM aa*H J. lanaand pwpMa. plan ini mHk radwin HradyUp aid atiaffcy at wMta r* IcMapA 1 mi 21. Spina dniauad ftan .14S|/tNfts 1131 s/iiei Mp4.1). Vn aid Kaawn Ua pmaal fcMUttlMW--*--aw--nn*WH4wiam4.inmAIn^ 4Mw--4 *.*>*--mpw WMI, 1970), Germany (Fiuczynski and Wend* land, 1968; Koetnan at al., 1967), Great Britain, (Holmes et al., 1967; Presst and Jefferies. 1969: Press! et al., 1970; Holden and Marsden, 1967), Netherlands (Koeman et al., 1967: 1969), Sweden (Anony mous, 1966; Jensen et alM 1969), and the United States (Anderson et al., 1969: Risabrough et al., 1968: Ri'ebrough, 1969).. Biological Magnification No datailad studies, such as those for DDD at Clear Lake (Hunt and Btschoff, I960) and DDT and its metabolites in Lake Michigan (Hickey et al., 1966), have yet been made for PCBs. , The. most detailed studies currently available are those of Jensen et al. (1969). The figures (mean, range of values, and sample size) given -in the table below are taken from their paper. PCS* Ippm hi ntncoMp toil BtMp StactMn ArchipU** Msntt Hafftae SMl OO.M.M t* J(0.S-2J) <ti J4(M4> ( )t V10*.7tt> J I(JJ-I.S) (IS) I 4) | )) OaOltwn Mi 230(|40>MON -- Brail III Him MMO(S400>I7.000)( 4| io(40.iwm ( d S4t(UO-0O) ( S) woo ( I) The levels in three species of fish in Clear Lake in 1968 were 0.03-0.005 ppm (wet weight) compared to 0.098 ppm in the breast muscle of a western grebe (Rise brough et al., 1969). Anderson et al. (1969) found that in most fish extracts the levels of PCBs were less than 0.1 ppm. whereas the levels in the eggs of cormorants (Molacrocarax ourtfus) were 5-9 ppm. Press!, Jefferies, and Moore (unpublished) found that the livers of fish-eating bir<' in the British Isles ranged up to a maximum of 900 ppm (wet weight), bird feeders up to 70 ppm, mammal eaters to 50 ppm, and insectivores to I ppm. Unfortunately, no average values or prey items were in cluded. The physical properties of PCS and the available residue data clearly indicate that these materials are capable of bio logical magnification up the food chain. 962 n;Ae>;. -OT S T?40 SNOM ftitio of DOT to PCB Rtaebrough el at. (1968) and Risebrough (1970) have examined ihe ratio of total DDT, f.e., DDT and its mctubolites to PCB. Me has found that the ratio DDT/ PCB was ('2 in San Francisco Bay and 5 10 for seabirds in the Pacific: in the Gulf of California, a region relatively remote from contamination, the ratio was 9*10. Vermeer (quoted in Reynolds. 1970) in western Canada found a DDE/PC9 ratio of 7 for California gull tissues and IJ for great Wue heron eggs. In the Baltic the ratio waa 1*2 (Jensen et al., 1969), al though along the west coast of Sweden the ratio was as low us 0.15. In grebes in the British Isles the ratio was 0,4-0.8 (Presst and Jefferies, 1969). For sea-bird eggs, Presst et al. (unpublished) found ratios of 0.06 to O.S. The overall impression is that the amount of PCB in tissues tends to paral lel that of DDE, at least in local ecosys tems, and the DDE/PCB ratio is lowest gear industrial areas suggesting that PCB it not carried quite so readily to remote areas. Nevertheless, the variation of the ratio is small enough to suggest that the routes of dispersal are similar. Since the evidence points to aerial fallout as the route of dispersal of the chlorinated hy drocarbon pesticides (Riaebrough e! al., 1968: Frost, 1969), it is likely that this is also the main route for PCBs. The path ways by which PCBs escape into the eco system are poorly known, although the possibilities have been recently discussed ct some length (Risebrough, 1970: Rey nolds, 1970). Since a large number of plastics and resins may contain PCBs (Table I), the most likely route is combus tion of these materials. This supposition remains to be tested. The possibility that PCBs could be derived from DDT should also be considered. The possibility that this conversion occurs in tissue is most unlikely for two reasons. First, it has never been detected despite the detailed work on the metabolism of DDT. Second, the only mechanism likely to give rise to a biphenyl is via free radicals and this is unlikely to occur in tissue. However, in the atmosphere under the influence of UV light, such a breakdown is more prob able. A possible reaction is shown in Figaro 1. Tautomeric shift could lead to a variety of isomers of dichlorophenyl, but it is difficult to envision the formation of more highly chlorinated biphenyls by this route. Since PCBs extracted from biological material match well with higher Aroclors (t.e., 1254), it seems unlikely that PCBs found in nature could be derived from other materials. Significance of Current Lcrels In view of the similarity of PCBs to DDT and its metabolites, the addition of PCB residues to (he environment is rough ly equivalent to an increase of DDE resi dues. However, since a synergistic effect of PCBs on DDT has been demonstrated in insects (Tsao et al., 1953), this pos sibility should not be overlooked in higher organisms. The enzyme induction effects of PCBs have been weil documented, and carbonic anhydrase inhibition is likely. The effect of PCBs on photosynthesis is a critical experiment that has not been done. Wurster's (1968) experiments with phytoplankton should be repeated with PCBs. The most critical area for research on PCBs is to discover the major source(s) of escape into the environment. Legislative control of a material escaping as a side effect of its use may have a different set of problems than the control of pesticides which are broadcast as a function of their normal use. The evidence suggests that it is important to find the leak and stop it. ' Acknowledgments We are grateful to Dr. Koemsn (Uni versity of Utrecht), Drs. 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