Document Yj5MyoDv0zk7Yvw0YGGN0JKnN

Polychlorinated Biphenyls ^ Another Long-Life Widespread Chemical in the Environment David R. Peakall and Jeffrey L. Lincer The recent finding that pelagic birds dying on (he const.-* of Great Bntran had polychlorinated biphenyls (PCBs) in their 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 basie- structure- of PC Us is show i; in Figure I. Any of the positions marked with an cun be substituted by chlorine. Widmark (1903) has calculated that of the 210 possible combinations 102 arc probable. His criteria for the.-., lim itation.; 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 Aroclors (Monsanto Company Trademark) arc des ignated by number* (Monsanto Technical Bulletins). The first two digits represent the molecular type: 12 - chlorinated bi phenyls; 25 and <14 - blends of chlorinated biphenyls and chlorinated terphenyls (75^0 biphenyl and 60% biphenyl, re spectively); 54 - chlorinated terphenyls. The last two d;gits give the weight per cent of chlorine. Thus, Aroclor 1242 is a chlorinated biphenyl containing 42% chlo rine. T he biphenyls commercially avail able from Monsanto range from 21% to 68% chlorine. Mass spcctrographic studies of Aroclor 1260 (Koeman et ah, 1969a) show the presence of 11 isomers; five con taining six chlorine atoms, five containing seven chlorine atoms, and one containing eight. Bugley et ul. (1970), studying Aro clor 1254, found IS compounds: one con taining three chlorine atoms, four contain ing four chlorines, four containing five chlorines, five containing six chlorines, and four containing seven chlorines. Thus. "Hi* juffrvn jrt cvfrcnllj Jt the Ljfljnwtr Ljiorjlvf). Cornjfl Ithaca. P*.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, adds, 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 zkroclori 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 nK'ul the biological decomposition oT PCBs, but it is likely that they arc more stable than DDT and its metabolites since they lack the ethane component between the. aromatic rings, which is the site of action of most of the transformations of DDT. Thus, PCBs have the necessary physical and chemical characteristics lor persistence and accumulation up the food chain. Use of PCBs Polychlorinated biphenyls were first de scribed in the literature in 1881 (Schmidt and Shultz, I3S I), and the successful com mercial production w-as achieved by the PCS Swann Company in 1930. In that year the physicjl characteristics and commcncal possibilities of these materials was de scribed by Penning (1930). PCBs arc now manufactured by Monsanto in the United States (Trade name Aroclor). PiodeUe in France (Phenochlor). and Bayer in Ger many (Colphcn) Other manufacturers are located in Japan and the So; id Union. No figures of the amount of these malerials produced annually are available, but to judge from the uses listed in Table 1 they may be very large. T he uses listed in the table arc only suggested apphc.i'iurt* taken from Technical Bulletin 306 of the Monsanto Chemical Comp.'.r.y, ur.d again there is no information on the extent to which these recommendations are acted upon by the manufacturers of plj*ii,s and resins. The u.sC of highly chlorinated Arc. lot* for extending the kill-life of forma1 j;i ns containing cklord.me, aid.-in. anj die',.I. in are mentioned under uiiscellunecu > appli cations of Aroclors. This possibility he* been considered in a number of papers. Sullivan and llornstein (1955). I lorn -lein and Sullivan (195 3 ), and T sao el al (1355) found that the chlorinated terphenil Aro clor 5460 increased the residual per.i,lenee of lindane. Tsao cl al (i`)55) -.on -idered lhal there was some indication '.list Chlorinated polyphenyl may have u syner gistic effect with lindane. Duda (1957) H aa out X PKieU POtftn ?Or. S^stituhou of Ccxofcme. <A> DSW 026758 Fig. 1. 0*CHLOPQO\rmr m a vCruvturt of l'Cl>S \ A) and possible reactions of I'Ctt-* i Ft i 958 BioScicrrcc Vo! -0 No 1" STLCOPCB4010719 sprayed elm sapling-, with a lindane v .10clor 5460 mixture (1:4) ami then tested the residual effect on ?he lease. 10 infes tation with elm leaf beetle (Galenicclla xunthoniclaerw). Me found that leaves treated with lindane plus Aroelor were protected longer and that llie insecticidal effeet was mure rapid than with lindane alone. Peaks corresponding to Aroelor 5460 have not been detected in the envi ronment. However, under conditions of temperature and How-rale communis used for gas chromatographic analysis these compounds would not be detected (Reyriolds, 1970). Nearly 25 years ago it was noted that Aroelor 1247 was one of 175 compounds out of 6000 tested that was effective against mosquito (Acgyps) larvae (Dconier cl al., 1946). Lichtenstein et al. (1969) tested the effect oT adding a variety of bipl:eri)ls and tcrphcnyls to DDT and dieldrin with respect to their toxicity to house and fruit flies. It was found that PCDs had very low toxicity to house flies when given alone but TCBs increased the toxicily of divhlrin and DDT. especially the latter. "I he effectiveness of these com pounds decreased ns the chlorinated level increased. For example. Aroelor 1221 in creased |l". raoi' 'lily nf fra:' Pi-'s from 59ro to 93rc. whereas Aroelor 1268 increated it to only 77'o. Analytical Methods I) Identification. Since various com pounds with electron-capturing properties have been tentatively identified in atmo spheric samples in the past (Abbott et al.. 1966), and some pesticides jre capable of hybridising in the soil to form a new com pound (Martha, 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 gas chromatography and mass spectrom etry has been carried out by three' inde pendent laboratories in Sweden (Widmark, 1967), Holland (Kocmun et al., 1969a). and the United Stales (Bagiev et I.. 1970). Widmark's report states that all peaks were identified by mass spectrom etry (although no data were given), but Kocmun and co-workers gave full experi mental details, and Bagiev et al. (1970) demonstrated that most chemicals in the eagle samples examined were components of Aroelor 1254 Thu., despite a recent statement by the Monsanto Chemical Company (in Riscbrough, 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 technique, preliminary tu qujntitalion of residues in samples com.lining both PC Its anj chlo rinated hydrocarbon pesticides fall mlo two groups those necessitating the de struction or alteration of one or more of the compounds, and those which do not. Included in the first group is nitration. Treatment with a 1:1 mixture oT sulfuric acid nitnc acid at 0 C for 5 min dexirovs or allots uldrin, p.p'-DDT. p.p'-DDD (TDD. 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 BMC (Jensen and Widmark, 1967). A more rigorous nitration with a 1:1 mixture of sulfuric acid-fuming nitric acid for 15 min al room temperature re moves, in addition to D!>T and its related products, uldrin, hepiachlor. Kclihane. Pcrllunc. Tedion. Telodrin, and Trilhion while lindane, hepiachlor epoxide, toxupliene, and Strobane are not removed (lirro et al.. 1967). Riscbrough et al. (1909) reported that this nitration also removed the chromatographic peaks of PCBs. Rey nolds (1969) repotted that his attempts to nitrate samples were nut fully successful in that there appeared to be loss of some of the more volatil-- PCB- while pc iks with longer retention times appeared. Armour and Burke (1969) reported that complex chromatograms resulted after nitration which could not be reljted to the unreacted DDT-F'CB mixture, and nitra tion was not pursued as a practical means 0f separating DDT and I'C li ior p...,. tests. ' Sepon 1 ficj I 'on with ulc''li.jt,_ \.Oj| , KOII will dehy rodroclilonn.ite Pc-;i-r,. Tox.tphene, DDD. and Dljp M ri_.. spective olefins (Archer li net Lr-islu. 1966: Klein and Walts. I9r,.|| et al. (1969) reported that PCB peaks are not rcmuvcJ or disp|.,..cJ hut :.u: no data. The second, anj in sonic ir\,:.i,:.r, more desirable, group of .mulsii. .1 tesli- niqucs allows the spcc.il sep :r lion of many chlorinated hytlioearbon pc a ici-lc, from PCB'. Reynolds (1969. |97oi r.,-. ported un an activated florisil solum:' technique which separated hepushi";. uldrin. DDL., and PCB with the firs', elu tion (6d ml n-hexane) front lindane, he;1- tae'hlor epoxide. DDD, and DDI with the second elution (40 ml 50'9 ethyl ether in hexane). Armour jnd B-Jike (I9?,)i Je.el oped a method atili/i.ng a silicic jsid- Cclilc column eluting uldrin anj PCB with the first fraction ( 350 ml petroleum ether), and lindane, hcpla-.hlor. Imp;a- elilor epoxide, dieldrin. endriti. p.p'- DDT, o.p'-DDT, p.p'-DDT. and p.p'- DDD with the second fraction (.'un mi acetonitrile hexane methylene chlutwlc I:I9:S0). Koenttin et al. (I969j). using, an activated HorLil column, eluted the jp - lar compound- including DDI and PL H with hexane, and then d.eljrin .mil end. ,11 with 10a diethyl ether in hexane. Mu! hern (I96S) reported on a me:hud which utilized silica gel-eoa'ed thin-lay - r plate's 1 mi 4 paK.V? -*iW V#'-fli 1 Ui'fe.rf Ml oVeh Vnhf 1* 4jU> i*4 a it % H/frati tW*rr4 WW nl 1784 4 1710 (7 I'd IwailUtH Uc'M'i Nn*i< MtUU iMrhv <!< 1717 | >*J AfKHf 17/1. i/)t ltI I1ISJ Arad* UW (IIS) 4*i- I72t I lid kwtm 1 Ml H4IIS) till |i 79-.( 177' irvi IIV* (VllSI A,pdm 1211 CM IIM |t t'.l kitOm 12*7 IV59M *4 mwdc C* pUi'-cs.'i. t (Bsl " nk H p nrtin hutiia eh r U t-4 l/fntti tfd k*^st K*4 u>i <*cj Oirn' sO fN4 O X o') Q 1 242 IIM September t. 1070 STLCOPCB4010720 t ,1 and a hexune/ethyl ether (98.2) solvent fact many of the original samples con epoxide generally represented a muj.i.-lu system. The plait,-; were developed, tained little or no p.p'DDT, it was pos of the apparent values. Before and alter sprayed with a silver nitrate solution, and sible to estimate relative PCB value,-. values for p.p'-DDF and dieltlr-n were exposed to UV light. The plate- were then divided into five horizontal sections. Dicldrin, endrin, V-DIIC, hcptachlor Ander-on and his co-workers also saponi fied sample- to remove interfering p.p' DDT and p.p'-TDL and then quantitated not significantly different. Ob-toti-ly. the magnitude of error may varv- dependme on the trophic level -urnplcd an-J cert ini- epoxide, p.p'-DDD. p,p'-DDT. o.p'- PCBs as Aroclor 1254 by relating sample with the area from which a sample t- col DDT, and p.p'-DDC (in that order) were peaks 9 and 10 to the corresponding peaks lected (Risebrough el al.. 1968, Jensen et found in the first four fractions, while of an Aroclor 1254 standard. Reynolds al., 1969). Since the publishing of ade most of the interfering compounds found (1970) employed a methud similar to quate separation techniques, there is no in wildlife samples were found in the fifth Koeman et al. (1969a) but based his quan reason why there should be any error in II zone. Bagley et al. (1970) used this meth titation on nn average of two or more pesticide quantitation contributed by od but mentioned that zones three and peaks. In addition, his results were re PCBs. ' i four contained practically all unknown ported as Aroclor 1254 or 1260 depending components as well as p,p'-DDT (zone on the overall pattern of the chroma Toxicoingy three) and p.p'-DDE (zone four). Armour tographic peak profile. It is clear that we and Burke (1969) used precoated (alu are still relatively unsophisticated in our Despite some recent studies, the lo\i minum oxide) sheets and n-hcpijnc and PCB quantitation methodology and will cology of PCBs remains rather poorly 2% acelone/n-heptanc for solvent sys continue to estimate only relative amounts known as compared to that of the chlo tems. PCBs (Aroclors 1254 and 1260) and of PCBs in field samples until we synthe rinated hydrocarbon pesticides For ex DDL were not separated, but p,p'-DDT size the individual PCB components com ample, no definite work has been done to and p.p'-DDD were completely sep monly found in the eeo-ystem and are establish I.D50 values for the variou. arated from PCB by both solvent systems. able to speak in terms of these individual formulalions of PCBs. Another possible means of separating in peaks as w; do for most pesticide residues. 1) Acme, single dose experiments terfering substances is to use a series of However, it has been kindly pointed out Tucker und Crabtree (I97U) found that a differing polarity columns in the gus chro (Risebrough, pers. comrn.) that, with ref single dose of 100 mg/kg Aroclor 1254 matograph at the time of determination. erence to biological significance, the cor (stomach tubeJ in oil) was fatal to moa .it This is less time Consuming and may be rect order of magnitude and accurate rela of three rats, while 500 mg/kg not useful when operating condition- can be tive amounts of PCB give the essential fatal to three rats. Aroclor 126S killed one selected such that PCB peaks are ab-ent information. This is because biological rat out of three at 500 mg/kg. 1000 mg,' in the region where auc./.; p::t^:!es effect sr; :h as ervy m- i-rh.-jinn, are re kg. 2000 mg/kg. and 40'>n rr.g-k;: Smyth emerge (Simmons and Tatton, 1967). lated to degree of chlorination, and the (1931) found that a 4 g/kg (degree of chlo 3) Quantitation. Koem.ni ct al. (1969a) existing nielhoJs give some indication of rination not staled) w js non to ce in eu u- \ semiquantitatively measured the residue- this activity. Therefore, that information pigs and rabbits, but this appears to be i in Japanese quail fed phenochlor DP6 by would be lost if stress were placed only due to the fact that material whi^h was using one of the peaks in a phenochlor upon quantitating individual peaks. given as a paste passed through the intes DP6 mixture as a standard. Risebrough 4) Magnitude of Error. Ever since PCB tine unabsprbed. Tucker and Crabtree (1969) quantitated relative level- of PCBs peaks were recognized for what they are, (1970) found that Aroclor 1242, 1254. by assuming that c.ich PCB compound residue chemists and other researchers 1260, and 1268 at a dose of 2000 mg/kg i produced the same pejk height with the interested in pesticide residues have was not fatal to mallard ducks (four ii electron capture detector as the same asked what magnitude of error is likely to groups of three birds each). amount by weight of p.p'-DDF. After result from ignoring tire presence of 2) Acute, /ceding experiments. Mon summing the heights of the individual PCBs. Only recently have studies either santo Bulletin 306 states that IPO ppm peaks, the total was multiplied by a factor directly or indirectly resulted in an esti diet hud no effect on rats, although no derived from measurements of standard mate of this error. Anderson el al. (1969) details of the studies were given. The ex solutions with electron capture and micro- quantitated p.p'-DDE, p.p'-DDD. and periments of Bennett et al. (1938) in wh eh coulomelric detectors. Jensen et al. (1969) p.p'-DDT in five egg samples before and 0.05 g/rat of 65D chlorine biphenyl was reported PCB amounts as the sum of all after saponification. There was no appre given orally every other day led to 50": PCB components und based the estimate ciable change in the p.p'-DDF, but ap mortality. If one assumes a body weigh', on a combination of mass spectrometry parent p.p'-DDD was reduced by ap of 200 g, then the alternate day do-e is and microcoulomelric and electron cap proximately 58% and p.p'-DDT by 90D. roughly 250 mg/kg, which can be com ture detection. Even with this elaborate Reynolds (1970) looked al a large number pared to oral LD50 for DDT of I I 3 mg kg approach, these investigators suggest that of samples before and after his PCB- (Frear. 1968). Miller (1944) found that DSW 0 2 6 7 6 0 the method is still rough and may be cor Florisil separation and found that the two oral doses of 69 mg of 42D chlorine rect only within a factor of 2. Anderson et actual p.p'-DDD residue (relative to the biphenyl a week apart were fjt.d to gumea al. (1969) devised a method for obtaining apparent residue) represented from 0 to pigs. Al an estimated body weight of 4'h) a crude estimate o( PCB residues as Aroclor 1254 from chromatograms where sep 790 in California gull (Lams occidental!!) g. this gives a dose of 170 mg/kg Tucker fat, 0D in cormorant (Ph.dacrocora.x auri- and Crabtree (1970) fed rats diet-, coot lin aration had not been attempted. On an lus) eggs. SOD in 10 pooled mallard (.4nas ing 10 and 1000 ppm Aroclor 1254, One empirical basis, it was found that Aroclor platvrhvnchos) duck eggs, and from 0 to rat out of six on the low d.w; died ih -. 1254 could be quantitated by considering 1049c in great blue heron (Ardea einerea) mortality was considered to he due tu peak 10 as p,p'-DDT and multiplying that eggs. Respective values for p.p'-DDT other causes. Four out of four of the lug'' value by 10. Since this peak had originally were 0 to 53D, 13 to 41D. I00D, and 18 to group died within 53 days and the cal been quantitated as p.p'-DDT, and in 102D. Actual residue levels of heptachlor culated intake was 1330-1520 mg kg 1 h . 960 BioSeicnec V.j' go \.- ` STLCOPCB4010721 (j food intake of the IOOO ppm gruup w* ' only 791# of the control group. Press! el al. (1970) fntve examined the toxicity of Aroclor 1259 !0 Bengalese finches (Lonchura striata). This is a difficull species for which to calculate the dietary intake. Due to their dependence upon unshelled food, it is only possible to present the PCB-laden food for a few hours a day (Jefferies. 1967). Loss by evaporation and loss by spillage roust 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 the case. Presst et al. (1970) also measured the con centration oT PCBs in the liver, they found that the range was large (i e., 70 697 ppm in' birds that died compared 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 ct al., 1963: Stiekel et al.. 1966: Stiekel and Stiekel, 1969) have con sidered that levels in the brain are a more reliable indc\ of toxic levels than those in Che liver or whole carcass. Dc Vos and Koentan (1970) fed Plicnoclor DP6, Clophen A60, and Aroclor 1260 to chickens at a dosage of 400 ppm. Mor tality was complete (20/20) for those birds on Phenoclor in 12-5S days and in 13-29 days for Clophen. The mortality Tor 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 a)l 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 cn be compared to 50-80 ppm for DDT (Stiekel et al., 1966). On the basis of this work. PCB is I/4-I/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 is borne out by subsequent work, it would suggest that differential absorption from the gut or differential penetration of the blood brain barrier is involved. The liver values were more variable. There was a considerable number in the 21X9-400 ppm range, but there were several values in excess of 2fk'"9 ppm. This finding is in agreement wciih the findings of Dale, Stiekel. antf co-workers that the brain levels are the best indication of acute toxic levels. McCune e; al. (1962) found no mor tality with eh.'-^kens fed 100 or 200 ppm Aroclor 1242 in their 'diet for a 4-week period. On diets of 400 ppm and 80(9 ppm. the me-rtalitics over a 4-weck period were, respectively, 50% and 90%. During the first 3 weeks, the mortality figures were 10% and 50'i. respectively. Flick et al. (1965). using the same material at 400 ppm in the (i el. had three birds out of 24 die in a 3-x"k period. Koernan et al. (1969a) fount5 that a diet containing 2000 ppm Phenoo'or DP6 caused complete mortality wit'.- Japanese quail (5/5) in 5 13 days and re.ts (8/8) in 1-56 days. Schocltgcr t unpublished) found that the 96-hr 'TLm for Aroclor 1221 using cut throat trout was 1.2 me/'I and for Aroclor 1260 was 6C.9 mg/1. In general, they found that r.vte toxicity of Aroclors was inversely proportional to their percentage chlorination c:nd directly proportional to their solubil.'ies. These figures suggest that PCBs acc two to three orders of mag nitude less U <ic to fish than DDT. Work by Lichtenstein et al. (1969) on house and fruit flies focmd that PCBs were 40-500 limes less t-.xic than DDT. the toxicity decreasing :i; the chlorine content in creases. Thtx.-,, it appears thal the lower vertebrates cmd invertebrates are much less susceptible than mammals to direct toxicity from PCBs. 3) Snbieth.il effects. As with the chlo rinated h>dr,.'carbon pesticides, the most important effects arc long-range sublcthal effects. The pathologic changes in various organs are summarized in Table 2. The table shows, some interesting differences between ma-.mmals and birds. The most striking finds in mammals arc alterations to the liver, whereas fluid in the peri cardial sac. Vidney damage, and reduced spleen was found in birds. McLaughlin et al. (1963) found that 25 mg Aroclor 1242 injected into the yolk sac of chicken eggs caused complete mor tality, whereas 10 nig caused 95% failure and teratogenetic effects were noted among the young thal hatched (beak deformity, edema, and growth relardant). Induction, of hepatic hydroxylating en zymes has iaeen demonstrated in the pi geon (Ri.scbroujh et al.. 196S). rat (Street et al.. 1969.1. and American kestrel (Falco sparverins). (Linccr 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 jexobarhil.il. in vitro rates of a11,J,nc ^ . droxylalion and demelh) lalion of p-nniuani.solc. and the rate of excretion of dieldrin. These workers studied II) cuntpounds ranging in chlorine content from 21% to 68% and found that all the effects increased with increasing chlorine eontent. For example. 50 ppm o( Aroclor 1221 reduced hexobarbit.il sleeping time by 11%. whereas for Arcelor 12-lX and 1268 the figures were, respeeti-ely. 35% and 48%. Thus, the suMclh.il efiems 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 die! and also demonstrated increased levels of cytoplas mic RNA with the higher dietary level using a cytophotomclrie technique Tucker (unpublished) found that a sin gle oral dose of 500 mg/kg Aroclor 1254 caused regular egg laying of Japanese quail (Commix cornrnix) to turn first to scattered egg production and then to stop completely for a week. The scattered egg-, had shells 9% thinner than normal, but thickness returned to control values "hen regular laying was resumed. Mallard decks dosed with I0(V1 tvg/lm of Amclnr laid one or no eggs before stopping for l2 weeks. The few eggs laid after the sin gle large dose of Aroclor had shells IX% thinner, and again eggshell thickness "as normal after resumption of regular laying The period before egg laying has been noted to be increased in the ring do- e (Peakall. unpublished). It is possible that the mechanism invoked is increased rate of metabolism of circulating csirjdiol in the liver (Peakall, 1970). Anderson ct al. (1969) had suggestive evidence that PCBs affected eggshell thickness, al though to a less extent than DDF.. Pre liminary results with ring doves support this conclusion (Peakall, unpublished). Levels of PCBs Fount) 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 several tissue samples and eggs of wild bird- in Great" Britain. The first identification of tha,e materials was by Jen,an and it is stated (Anonymous, 1966) that residues in feath ers collected in Sweden go back to 194 1 PCB residues have been reported in w,!Jlife from Canada (Holden and Mar-,!-". 1967: Anderson ct al.. 1969: Reyn i!2-. September !, 1970 DSW 026761 96 1 STLCOPCB4010722 TABlE 2. Pathologic changes induced by PCBs Animal lie at Ardnay Paricardurm and Paiiloneum Other Observable Change* Rf*i tnen Imjle sol dot* 1 63 mg (42% d) Quin** Pig fUt Rabbit Small tat droplets through lobufaj. slight to moderate central atrophy, focal Meroiis naiad in a few Animals. EnwUjjlJy normal No nataworthy changes Adranjls, tpfa. and pancreas showed no Mteworthy changes. Miller (1344) 300 rig dally fa* < AayO |E 5*. Cl/ 10 mg daily hr Up to 6 months Cl) Rat put Cells swollen. h/shne granules present, most died v.ilhin few days. Enlarged (J3S weight increase), large number of hyalin* globuies to cytoplasm. Several died during tsperimenl. lennti at al. (1933) lanneK 26. SO, l 100 ppm in diet for 15 day* (21-43'. CJ Araciora) rji taieasa in weight, effect . increasing with increasing 1 chlorine content Aroclor 1232-10", 124?-I2r., 17S414%. 1268-24', at SO ppm. Street ai al (In press) tOO ppm In diet 20C ppm in dial 400 ppm in dial 100 ppm in dial (Aroclor 124?) Chicken No effect No effect Enlarged and molded Damaged 2C0 & ppm in diet for 3 walk; (42V Aroclor) Chicken No changes netto Damaged Slight Hydioperica/tfiu n Hydropet icardiuiTi HydfOpericardium. hydroparitC'ieum. Enlarged. fwlanan al 200 ppm. eitemivi fcemonbage, and enlargement at 400 ppm. increased fluid in pericardial sac at th; higher concentration. Paleness of pancrau, enlergsmcni of adrenal and small spleen at low concen trations. At fiighai concen trations pale cidJm-nlorsd iuibhalg McCun* at at. (195?) Flick it II. 11965) Various doses (S4S D. Aiodor] Bengalese finch No weight changes Weight was 32 4% of train weight (or ccntrola and S3.SS (or those dying hm PCB poisoning. Slight w light increase, a few showed liquid m pericardial tac. RrliJt It ll (In P'sll! 400 ppm in Sat lor SO <hyi (SOS CD ChitViit Ctntrolnbalar necrosis (cenpd 1 and 21. Liver , weight increased from 2 ?6 g/lCM g fo 4 21 g/103 | (compd. 31. fall/ degen- ralion. Tubular dilatation, [compd. \ sod 2) Rate with tDTTipd. 3. Hydroparicardium common with compJs. 1 and 2. Rare with compd. 3. Increased pn-phyria, small -.vrth icd jcir-n cf red pt.'p and a'.tovhy ol while p !p (compd 1 #nd 2). S;!eert djcea'J. from 0.146 g/IQO 3 tbO.13: gMOOg. compd 3). Vos anj Kuin;, i (In pie:s) *etwc:' OP I |UM I). 4JO 1) tr4 Arader 1JS5 I J| wtt, wW frfami'U t(l* **ttl 4H efc<i*t (H n <tm;4 l *S 1 mHm ID tfm h, | |\ *inMy *o DSW ]. 026762 1970), Germany (Fiuczynjki und Wendland, 1968: koerrun et al.. 1967), Great Britain, (Holmes et al., 1967; Presst and Jefferies, 1969; Press! ct al., 1970: Holden and Marsden, 1967), Netherlands (Koeman et al., 1967; 1969), Sweden (Anony mous, 1966: Jensen et al.. 1969). and the United Slates (Anderson et al., 1969; Risebrough et al.. 1968; Risebroueh. i969).. Biological Magnification No detailed studies, such as those for DDD at Clear Lake (Hunt and Bi.-vehoff, I960) and DDT and its metabolites in Luke Michigan (Hickey et al.. 1966). have yet been made for PCBs. The most detailed studies currently available arc those of Jensen el al. (1969). The Figures (mean, range of values, and sample size) given in the tabic below are taken from their paper. PCBs (ppm m txuacuble fjO Sal lie Stockholm Vrchipdj|o Musvt 4J (| .9-1,6) (JO) 52(3-1-7-0) (15) Hemnf 4.8(0.5-23) (18) 5.1(3.3-8.51 (4i Scat W(I4-UI ( n MU4-S6) ( 3) Guilttmos cut 230tl40.J6UH % While-tailed Eaj/e -- fectural muscle |r jin E|J Heron ^ -- -- -- -- U,(TO (*Jnr). I7.UOUI ( 4) 410(400.1500) ( 3) JJOCJO-JOOI ( 51 %00 ( 1) The levels in three species of fish in Clear Lake in 1968 were O.OJ-O.OOi ppm (wet weight) compared to 0.09S ppm in the breast muscle of a western grebe (Rise brough el al.. 1969). Anderson et al. (1969) found that in most fi,h e\(raet> the levels of PCBs were less than 0.1 ppm, whereas the levels in the eggs of corntutants (/Vialacrucorax auriiiis1 were 5-9 ppm. Presst, Jefferies, and Moore (unpublished) fou-iJ that the livers of fish-eatmg bird, in the British Isles ranged up to a rrusimum oT 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 PCB and the available residue djta clearly indeale that these materials are capable of bio logical magnification up the food chain 962 BioSoicnsc Vi,-1 ZD Nc |t STLCOPCB4010723 Ratio of DDT lo PCB Riscbrough ct al. (I96S) and Kiscbroxjt.ii (1970) have examined the ratio of lotjl DDT, i.e.. DDT and T\s metabolites to PCB. He Has found that (he ratio DDT/ PCB uas 1-2 in San Francisco Bay and 5 10 for seabird-, 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 DDF/RCB ratio of 7 for California gull tissues and 13 for great blue heron eggs. In the Baltic the ratio was t-2 (Jensen et al., 1969), al though along the west coast of Sweden the ratio was as low as 0.15. In grebes in the British Isles the ratio was 0.4-0.8 (Presst and Jefferies, 1969). For sea-bird eggs, Presst ct al. (unpublished) found ratios of 0.06 to 0.5. The overall impression is that the amount of PCB in tissues lends to paral lel that of DDL, at least in local ecosys tems, and the DDU/PCB ratio is lowest near industrial areas suggesting that PCB is not curried quite so readily to remote areas. Nevertheless, the variation of the ratio is small enough lo suggest that the routes of dispersal arc similar. Since the evidence points to aerial fallout as the route of dispersal of the chlorinated hy drocarbon pesticides (Risehrough et a! . 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 at some length (Risebrough, 1970; Rey nolds, 1970). Since a large number of plastics and resins may contain PCBs (Tabic I), the most likely route is combus tion of these materials. This supposition remjins 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 Tor 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 lo 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 Figure I. 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 (i.e., I 254). it seems unlikely that PCBs found in nature could be derived from other materials. Significance of Current Levels In view of the similarity of PCBs to DDT and its melubolites. the addition of PCB residues to the environment is rough ly equivalent to an increase of DDL resi dues. However, since a synergistic effect of PCBs on DDT has been demonstrated in insects (Tsao et ah, 1953). this pos sibility should not be overlooked in higher organisms. The enzyme induction effects of PCBs have been well documented, and carbonic anltydrasc inhibition is likely. The effect of PCBs on photosynthesis is a critical experiment that has not been done. Wursler's (1968) experiments with phytoplankton should be repealed 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 ol 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. Koeman (Uni versity of Utrecht), Drs. Presst and Jef feries (Nature Conservancy, Great Brittan), Dr. Reynolds (Ontario Research Foundation), Dr. Street (Utah State Uni versity), and Dr. Tucker (U.S. Fish and Wildlife Service) for advance copies of important material. Some of the work presented here was carried out under NIH Grant F.S00306. Dr. T. J. Cade, Principal Investigator. 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O'G Tatton. 1967. Im proved gas chromatographic system* for de sis by marine phytoplankton. Samee. 159: 1474-1475. MICROBIAL CULTURES COMPLETE BSCS LISTING! GUARANTEED PURITY! OVER 200 SPECIES AVAILABLE I MOST ORDERS FILLED WITHIN 48 HOURS NOTICE t fl------ - BACTERIA and FUiiGI cultures------- $3.oo per culture ($2.50 par culture for order* of 6 or more cultures) C_____ CC 9 ZlilGPHACE -------- $4.00 per 5 ml filtered broth juipensions CitL / U Jt<t. I $------------Aveilobla at special prices COMPLIMENTARY CULTURES One complimentary culture (bacterial or fungal) will be included for each six cultures ordered. Compliments may be selected If so desired. Free CATALOGUE OF CULTURES Available Upon Request (PRESQUE I5LE MICROBIOLOGICAL ASSOCIATE -------- o P.O.BOX EOO/.m-iSQUE ISLE, PENNSYLVANIA 16505 Telephon* 814-333-6373 -# -O o. o o a 964 BioScicucc 'r ut 2f l' STLCOPCB4010725