Document Jv85p0XEJ9Rm92rZk4MpeMKxB

Introduction In IS06 Jense.n(1'*)' established that residues of polychlorinated biphenyl;. (P33s) were present in pike {nsox luciuo) and a white-tailed eagle . (naliaeetus albicilia) in Sweden. "his discovery, largely arising by cnance during studies an progress on ^a/4. am o--.cr crg^nocnj.orane 2 56c w..cades, vas whe . ar&w ^n>* .r.u .a^n kucw <#has group c* synthetic organic chemicals nay have become widely distributed in the environment. Immediately folio'.ring their identification in Sweden a programs of research was started in the united Xir-gdcn to ascertain if these sane co-pounds ere also present in wild animals in the British Isles. This v/ork not only confirmed that they were present but also that they were widespread. _ Poliowing this discovery Monsanto Chemicals Ltd., the sole nanuf&cturer of FCBs in the United Kingdon, introduced a ban early in 1971 on aVI ` non-controllable use of the PCBs. This paper gives an account of the investigations carried out in the United Kingdom to deal with the PCS problem, in the hope that the experience gained nay help ether countries which nay be faced with this type of problem. arising from the mar.ufacturc and use of these and other sirilar synthetic organic chemicals which are nor/ being manufactured in increasing amounts in nany parts of the world. ' Manufacture and Use . The manufacture of FC3s was first started by Monsanto in the United Stat-s of America in the early 19303 ana in the United Kingdom, at one plant in Monmouth in South Vales, in the early ii,5Gs. Prior to 1551 all the F'3Z ; used in the United Kingdon were imported. Initially these compounds we -e used almost exclusively in electrical transformers and then later also ii capacitors. - Because of their outstanding properties'as a cooling arid ~ heat transfer fluid, combined with extremely low oombustability, their prinsipal. use has remained in the electrical -industiy _whgre_theygreplecg "^ne~more combustible oil products. The position before the ban was int -o- duced in 1571 was that about half the .-33s sold in the United Kingdom we -t into the electrical industry, the r.-.r-air-uer being used as aaditives m p .antics, .resins. rubbers, adhesives, paints ar.d in heat transfer systems and hydr ulic fluids. There was also latterly some use on an extremely small scale i . vacuum pumps and in speciality lubricants. OSW 282548 STLCOPCB4063877 " IgjTnh? -Analgia- - Tha P53s are a series'of Compounds, the differences stemming Iron the - largo^uaber_rf_hcaDl^ir-3u'*si3. isomers which ore possible. These difrerent : fcoaologues and isomers ney have different properties. Cormeroial proCact3 contain large cuabers of the different compounds in varyir.r proportion.". FCBs are very stable chemical compouads resistant to degradi-ion by . . oxidation both cheaically end biologically. They are relan-vely insoifoie in water out are miscible with natural oils ana fats. Criy United information is available on their tonicity. . The acute IB f- value no 'ats, using's commercial product containing 42j chlorine, was found to be about 4 nl/^g. In other tests on snail mammals levels of 1-iC grn in'feedstuff had no significant toxic effects, hut atlGG pea there were icne indiea .ions ----- -------- ------ (2) --* .* of long-tern effects . Tho estimated dose rate for 5Ql n:rtaiity as 56 days feeding nrochlor 1254 to the Bongolese finch (Lonch-ra. striata) has been shorn to be 254 cg/kg/day, suggesting that in this igecies thi-. particular PCS has only 1/13 the toxicity of \ In tn; 'marine brewn shrimp (Crangon crangon) tho LC 50 for acute toxicity in 43 sours prove!' to be 0.3 ??m for FC3 compared to C.CCf ppu for It las also bipn shown that at low levels FCB, like BUT, can induce sterioid uydroxiiatirg enzymes in the liver of pigeons (Cciumba libia) and so nay effect their breeding capability^. The PCBs thus have many of the physical and chemioal properties of the orgsnochlorine insecticides and appear to produce similar toxic effects in a number of animals, although generally apparently having a somewhat lower toxicity. It should be appreciated, however, that because of the large number of FCB compounds, and combinations of these, that are now available, the toxicity of different types may vary considerably. Analysis for PC3s has been by use of gas chromatography, using electron capture detection with occasional" Identification and structure confirmati on by gas chromatography mass spectrometry. Because of the need to measure FC3s^at extremely low levels (e.g. -1 in ioj^or.less)j- ancLthe,similarit.ydAof their~chemica1 structure to that of the organochlorine insecticides which were frequently also present in the tissues of wild animals uncergcing analysis, great care was needed in the development of a reliable standard teohnioua that could be employed by separate laboratories to give compar: jle results. This was achieved in the United Kingdom by close liaison between the laboratories of the Natural Knvircnmeat Research Council; -he Kiris', .y DSW 282549 -2- . STLCOPCB4063878 - ` -y. ................... _______ of Agriculture, ?isheries ana ?cod, the Department of Agriculture and ` * Pisharies in Scotiand,and the central laboratory of the Government Che. at in London. This close liaison between the analytical chemists engaged hi ^ the investigatory work and the early establishment by then of standard methods to be followed, was a major factor in the rapid confirmation ana subsequent surveillance of the distribution and levels of PC3s in the British Isles. Distribution As they are persistent and fat sclubla the rCBs, 1'ike the orgsnochlcrir.: insecticides, are retained in thejtissuss_of animals. It was decided therefore that a good indication of the extent to which they had become dispersed in the British Isles could be obtained from an examination of fish, marine invertebrates and predatory birds (predators, because of th position at the top of food chains and because their diets include a wid range of different organisms, can be used to indicate whether or not residues are present in a very wide range of organisms). - Another factor which influenced the type of surveys undertaken was that '^'work v/as- already in progress in several of the government laboratories to investigate the levels of organcchlcrine insecticides present in fish - and predatory birds. It was, therefore, a relatively straightforward m atter to extend the analytical procedure to include the PC3s. * During the late 1960s over 500 predatory birds and their eggs, together with large numbers of fish and invertebrates from cany parts of the 'British Isles were examined for PCS residues. Some residues of PCS were found to be present in most of the specimens examined from a wide variety of localities, including remote mountain regions of Vales and Scotland as well as industrial areas. The amounts present wee not found . to be correlated with any particular geographical locality, but with habitat, the larger residues being present in aquatic species - both -- freshwater and marine. Thus the amounts present in the tissues of the essentially freshwater fish-feeding heron (Ardea cir.erea) included one 2^pecinen^with>og^0Qrpfa~-ofl7CBs^ih ;tha^ivarj.:'-3ihe7aiSthmetifr-ffiean of rthw 16 adults examined being 93 ppm. The levels present in 101 eggs of thi. species ranged from 0 to 80 ppm with an arithmetic mean of 5 ppm. Similarly, the fish-eating Great Crested Grebe (Podiceps cristatus) and Kingfisher (Alcedo atthis) contained up to 40 ppm. In contrast the lever, in tissues of non-predatoiy omnivorous and herbiverous terrestrial speci s rarely exceeded 5 P?m, with the bird-feeding terrestrial predators conir. betv;een the two^^. oiinn CoMo CM W Q STLCOPCB4063879 -Further confirmation of the presence of ?CB residues in the sea was obt. ined in the autumn of 1969 during an investigation into the mass mortality of over 12,000 seabirds in the Irish Sea. 7ihile no single cause for these deaths was established, the report of the incident concluded that "one c? . the most striking finds of the analytical programme was the presence in die livers of most of the dead guillemots (Uric aalgae) of unusually high le/els of PCBs". During this investigation the levels found in seawater (53 s .uples) was < O.Clpg/l; in zooplankton (7 samples) -<10-30 ys/ksi ^n mussels ( .hole, less shell, o 100 specimens) 10-300 and in 11 specimens of norway lobster (1'ephrops) < IG-ICO j^g/kg. The levels in the livers of fish an! seabirds (expressed as ^ig/kg) went up to 2,600 in herring (Ciupea haren. ;s); 27,COO in whiting'('ierlangiuo merluccius): 50,000 in ccd (Trisopterus minutus) and up to 600,000 in guillemetv. During the same period an investigation was carried out off the Cornish coast in the south-west of England into the deaths of about 40 grey seals (Halichoerus giypus) pups. The PC3 levels in 11 specimens examined were found to be relatively high (17-90 ppm in the liver, end 113-187 ppm in the blubber). It was ~ concluded hov/ever that FCEs v/erc not a contributory cause of death, which was attributed to normal juvenile mortality^ Pollution ar.d Manufacturing .. . These discoveries led to consideration as to how the residues of FC3 were getting into the environment. The highest levels being found in freshwater and marine species suggested that contamination of inland waterways and direct contamination of the sea must be major faotors. The most obvious ways in which this could come about are through pipelines from factories, as a result of atmospheric pollution following inefficient incineration. (the FC3 residues eventually being washed out with rain and again ending (S' up in waterways and the sea), end in sewage sludge dumped into the seav '. The results of the surveys of the distribution of FC3 residues however -gave no indication aa-to which; if arypof thesb irtTculaFYources*'nay"l.mve been primarily responsible for the existing pollution of the 3ritish Isli.s and while hdgheg levels .x^ve. been-fo^n^n^he:esj^jgu^gf-jjie^rive~ Clyfo___ *~anSoffrthe south west coast of Scotland generally, there is no outstanding use of PC3 produots in this area to explain this. .... -4'- DSW 282551 STLCOPCB4063880 "he residues most commonly found inr animal tissues have been of the highly chlorinated type. It should not bo concluded from this however that the c has been a greater use of this fora of FC3 ar.i thus by using less chloriu- ;ed types pollution by FCBs could be avoided. "hose results are more probably a reflection of the pattern of decomposition of FCBs once they enter the natural environment and probably all the FCBs contribute to environmental pollution. ' ----- She manufacturing process of PC3s is "dry", so that aqueous effluent is not a by-product. Contamination of waterways from industry must therefore have come about as a result of carelessness or accident, or possibly because -until-recently those concerned ".vere~unav:nre that these compounds could result in environmental contamination and so made no special provision for dealing with wastes containing FCBs. Provided that sufficient care .is taken to contain spillages and 1tsci/o*^6S SCVUT91 &Ijh cm w&X* manufacture during handling c.g. when the FCBs are being loaded^into drum;: or tankers, losses into drains and waterways can be avoided. The . . installation of sumps and interceptor pits in the factory drainage system, coupled with a regular monitoring of all effluent, should enable any loss from 'factories*to*be kept at an absolute mininu,. Conclote destruction by inciaceration can be achieved if a temperature of 800F? is maintained for at least 10 seconds. ' The Ban . Following the discoveiy of PCBs in the environment, the Monsanto Company itself is believed to have spent well over half a million pounds on its o'. :i programme of research into methods of analysis, identification and measurement of FCBs. Froa the beginning the company maintained close liaison with ti e Central Unit on Environmental Pollution of the Department of the Environment, the Natural Environment Research Council of the Department of Education ar.l Science, the Ministry of Agriculture, Fisheries and Food and the Departner.t_ Of 'Agriculture' and Fisheries in Scotland - the Government Departments most directly concerned with the control of environmental pollution and for offlduotin^^s^^h tm-iinrgarrtft visited the laboratories of these Government Departments where the actual field investigations and analyses were being carried out and discussed progress and methods with the scientists engaged in the work. They were thus informed of the development and progress of the investigations and were able to draw conclusions from the results at an early stage. DSW 282552 STLCOPCB4063881 Tiie-need for some fora of ban bet^S^ppareij^once''it had been dcmonstr:. cod that the PC3s were widespread in the natural environment and that the lc ,-cls present, particularly in certain aquatic species, had reached the point -..here undesirable effects nay bo expected. Because of their stability and thuir miscibility with natural oils and fats, it could reasonably be concluded that continuation of their use, even on the present scale, would result in further increases in the levels present in a wide range of animals, including seme used as food by man. ........... . .. .................... - The fadt remained however that because of their industrial properties, particularly their low inflammability, uhsy still had 3erne important (possibly vital) uses in industry, for example in certain elecuricai equipment covered by safety regulations which require the use of ' non-flammable fluids. A sudden complete withdrawal for all uses, in t.s absence of suitable replacement products, could therefore have serious consequences to industry and to human safety. fortunately, for most uses of thi3 type, the FCBs can be enclosed in sealed systems. This, coupled with the fact that by exercising care during _, "manufacture and transport losses could bo largely avoided and also that satisfactory methods of both biodegradation and incineration have been developed, led to the conclusion that a partial ban affecting only non-controllable uses would be sufficient to safeguard the environment. Accordingly from 1st ilarch 1971 Monsanto, without ary directive from the UK Government, introduced a voluntary ban on all uses where FC3s were not confined to a closed system, .f They axso made arrangements whereby in these cases where FCBs would continue to be used the responsibility for final disposal, after working life was over, would remain with the Ilonsanto Corpary and arrangements have been instituted whereby the equipment is returned uo Ilonsanto for destruction of the FCBs under controlled conditions. DSW 282553 &4Z STLCOPCB4063882 IDiscushion. The initial discovery that the environment wa3 "becoming polluted with pwj . residues case about largely as a result of chance. Until Jensen's discovery, nobody had suggested or even suspected that these compounds l \y be a possible source of environmental pollution and had the research on the organochlorine insecticides - during the course of which the discovery cf the PCBs was cade - not been in progress, it is cost probable ire would still not yet be aware that a PCB problem exists. As the aanufacture t ' PCBs is now undertaken in a number of countries, this leads to the .question: what other countries have a PC3 problem? This question can only be answered by an appropriate scientific investigation. To carry out an investigation of this type is an elaborate procedure, involving the employment of highly trained scientists and expensive, complex apparatus. Sven when and where these are already available, there is the need to develop a new analytical and evaluation procedure, which must then be agreed and adopted by different laboratories so that their results can bo compared, - - ... - . . . . . . -. In, the US the relatively rapid Banner in which the investigation of this problem was accomplished was very largely due to certain existing circumstances. These included the fact that (a) investigations into . similar problems involving the organochlorine insecticides were already in progress in several Government laboratories, with the important resulu that chemists and appropriate apparatus were already available; (b) a . liaison committee representing analytical chemists in the UK was already in' existence, so that agreement over a standard method of analysing the FQBs was established at an early stage; and (o) there was in existence a well-established scheme for the collection of suitable biological material for analysis from a large number of different geographical localities, including areas affected by unusual incidents involving large numbers of casualties.Without these circumstances, even an industrialised countr.v like the GS would have had to undertake extensive time-consuming and expensive procedures before investigatiqns_coid.d be _started._In the case._ 'dvTc^ah'^:counSy,:^e"rtbrs']c^KbulG. lia ^ornldableT -7 DSW 282554 STLCOPCB4063883 "Vft close' co-opcrapioa btQe Industry and Government that exists la the ' UK was another ittportaxct^fssctor In ta:g"&9gj5seg;,to"$hi8 problem......In* this particular case Konsanto were able to take independent action~at--a much*L earlier stage than would have been possible had the necessarily protracted m^mmm n --------rr- rn i irr-i-i. r ~t m~ i.- - r- ,_jt- . <r ___> Ul| . negotiations had to be undertaken with Government Departments before - legislation could have been introduced. One aspect that nay require further-attention exists because PC3s are manufactured in a number of other states, including both Western and Communist countries. It would obviously be unacceptable if the ban instituted in the UK by .Monsanto was . rendered useless by the importation of ?C3s from elsewhere. A further complicating factor in this question of imports and exports could arise because FC3s are often incorporated in electrical ana other goods. If a country banned the use of FCBs, including their importation, this would have the result of disqualifying a whole range of products from being imported into that country. Discussions have already been held between some of the international manufacturing companies and in 3ritain the " Government is retching the situation. But the trade implications of this specific problem, and the possible creation of non-tariff barriers _ if Governments find it necessary to impose statutory controls, merit discussion at -intergovernmental' lever. ' OSCD has alreddy instituted, ` for a triad period, am "marly Marking System" for controls or restrictions instituted by Governments on the sale or use of certain chemicals, although this does not cover unilateral action by industry unsupported by statute. The United Kingdom would welcome a discussion with other member Governments of the FCB problem, and a consideration of whether the "early warning" scheme could usefully be extended to this type of industrial policy. 02CD has, in addition, supported a working party on the analysis of organochlorine substances in the environment, and this group might be invited to consider what programmes of monitoring are desirable to determine how far the ban applied in the UK (and likely to be followed by others elsewhere in Europe) .is effective in reducing the levels of PCB in the --environment.-------------------------:--------------------- -------------- - 6 9 71 -8- QSV\f 282555 STLCOPCB4063884 ' (l) Jenson, S. (1966). "Report of a new chemical hazard". New Scientist, -1(32)612. . ... ... (2) Lidgett, R A & Vodden, H A (1570). "PC3 - The Environmental Problem". -' ' Report of the National Environment Protection Board, Sweden. (3) Prestt, I., Jefferies, B 3 & iioore, X V/ (1970), "Polychlorinated ` Biphenyls in '.7ld 3irds in Britain and their Avian Toxicity7. -u~ --- . Environmental Pollution, (l) 3-26. ' ; : - ' (4.) Portman, J S. Private Communication, quoted in (2) above. . (5) ' Risebrough, R '.7, Rieche, P, Peakall, D B, Herman, S G-, & Xirven, II X . (1968). "Polychlorinated biphenyls in the Global Ecosystem". Nature, London, (220) 1093-102. (6) Koldgate, J W (l97l). "The Seabird V.'reck in the Irish Sea Autumn 1969". . The Natural Environment Research Council Publications (London) Series C, No. W. ....... (7) Bonner, V/ N (1970). "Seal deaths in Cornwall Autumn 1969". The Natural Environment E.esearch Council Publications (London) Series C, No. 1 . - _- (8) Holden, A V (1970) "Source of Polychlorinated Binhcr.yl Contamination in the Narine Environment' Nature, London, (228) 1220-1221. ' DSW 282556 STLCOPCB4063885