Document zo8X9rKj7RyQ0GQ47D0DorgM0

MONSANTO CHEMICALS LIMITED PRODUCT TOXICOLOGY - AHOCLORS, Report suraraar.3ing present knowl'ad&e.jooticerning chlorine-containing residues in wild life and visits made to organisation implicated therewith during the teriod April 28th - May 1st, 1969. Circulation J.W. Barrett, London. R.A. Baxter, Ruabon. H.A. Vodden, Ruabon. H.R. Newman, Newport. A.C.W. Pemberton, Newport W.J.S. Budd, London. J. Herefousso, Brussels. D. Wood, Brussels. R .E . E.P. R.E. W.R. *rf.S. Keller, St. Louis. Wheeler , St. Louie. Kelj^y, St. Louis. Ri/fhard , St. Louis. Bergen, St. Louis. Formerly Research Services Manager, MCL, and now Consultant to MCL in the area of Product Toxicology and Safety the Use of the Company's products. TRAN 021762 STLCOPCB4024879 INTRODUCTION The vide agricultural usage of insecticides in the post World War II period and consequent effects on wild life have led in certain circles to apprehension concerning the overall effect on itn. The situation has been under study for many years and Government agencies and manufacturers of insecticides have been implicated in the various aspects, particularly in the assay of such residues in many species of wild life. Fish, fish-eating birds and mammals have been subjected to vide ranging study, and it became clear that terrestrial usage of insecticides could have far reaching and hitherto unsuspected effects on wild life, part of it making an important contribution to the diet of man and domestic animals. The size of the wild life specimens and the minute con centrations of insecticides therein demanded highly sensitive methods of assay, which have been progressively refined. Gas liquid chromatography using electron-capture or microcoulometric detection has become established as the most suitable technique. It appears that the chromatograms of the residues shoved not only the peaks corresponding to the insecticides and their knovn metabolites, but additional peaks of unknovn chlorine-containing substances. Towards the end of 1965 these unknown substances vere identified by SOren Jansen, a research worker at the Institute for Analytical Cheraictry, University of Stockholm, under the direction of Gunnar nidmark. Uaing a combined gas chromatograph mass spectrometer (LKB-9000) it was shown that the peaks are due to polychlorinated biphenyls (PCB's), The evidence and reasoning are available and the conclusion can hardly be in doubt. Unfortunately the announcement was coupled with sensational statements concerning the poisonous nature of the PCB's, which were calculated to cruse misgivings both to public authorities and to the general public. Jensen and Tfidnurk found PCB's in specimens of pike from different parts of Sweden, fish spawn, a dead eagle and in human hair, and even on fir cones'. The conclusion reached was that the PCB's originated from burning industrial wastes and were washed down by the min. Examination of feathers from museum specimens of sea biraa suggested that contamination commenced in 1944 . The original work of Jensen and Widmark has been extended and generally confir-od, notably by workers at the following establishments and much of the detail has been published:- TRAN 021763 STLCOPCB4024880 3 Great Britain 1. Laboratory o' tho Government Chemist, Cornwall Houjo, London, S .E._ . (Notably Mr. O'G. Tatton) 2. Freshwater Fisheries Laboratory, (Ministry of Faskally, Agriculture, Fisheries Pitlochry, Scotland. and Food) (Mr. A. Holden) 3. Tunstall Laboratories, Shell Research Limited, Sittingbourr.e , Kent. (Dr. J. Robinson and Mr. A. Richardson) .4 Monks Wood Experimental Station, (^Nature Conservancy) Abbots Ripton, Huntingdonshire. (Dr. N.W. Moore) Established by Royal Charter to (1) provide scientific advice on the conservation and control of the natural flora and fauna of Great Britain, (2) establish, maintain and manage natural reserves in Great Britain including maintenance of physical features of scientific interest, (3) develop research and scientific services related thereto. At 30th September, 1963 there were 144 scientifically qualified staff and in 1963--1 there was a Government^ grant-in-aid of 701,000. Holland 5. University of Utrecht (Professor H. Van Genderen) U.3.A. 6. University of California (Drs. R ,W. Riseborough, P. Rieche and S.G. Herman) 7. Cornell University (D.B. Peakall) 8. San Diego Natural History Huseum (M.N. Kirven) TRAN 021764 STLCOPCB4024881 This report is written following discussions with staff from Establishments l( 2 and 3 in which Dr. R.E. Keller and Dr. E.P. Wheeler (1 and 3 only) were associated. Drs. Keller and Wheeler are proceeding to visit 5, University of Stockholm, to see Jensen and Widaark. They are also visiting Bayer to ascertain its reactions as manufacturers of PCB's (Clophens). SUMMARY 1. There can be nc doubt that traces of PCB's (Aroclors) are to be found in wild life, fish and certain items of human diet. 2. There is little evidence to show how serious this minor contamination '.'ill prove to be, but what evidence there is is reassuring. 3. There is little evidence to show how the PCB contamination arises. It nay be by run off of wastes into rivers, or by burning of industrial wastes with consequent washing down by rain. It is remotely possible that the PCB's might arise by biochemical action on insecticides and other chlorine-containing materials which are similarly discharged into the rivers, seas and oceans. It could be that among the vast quantities of materials destroyed on land and at sea during the 1939--45 war, significant quantities of Aroclors and Aroclor-containing materials found their way into the rivers, seas, etc., and are being olowly released by corrosion, extraction, etc. (see footnote at end of report). 4. A considerable Monsanto effort will be necessary to obtain the necessary analytical and toxicological information for dealing with thiH threat to our commercial operations. A. Yisit to Freshwater Fisheries Laboratory, Pitlochry* Uonday, April Zoth, 1969 . " Mr. A.V. Holden - Officer in Charge. Dr. R.E. Heller - MC Dr. D.V.N. Hardy - UCL This visit was made not so much on account of contributions made to the subject but because Hr. Holden acts as Co-ordinator *Dr. E.P. Wheeler was prevented from taking part in this visit due to the sudden indisposition of Mrs. Wheeler. TRAN 021765 STLCOPCB4024882 / 5 for the programmes of the O.E.C.D. countries concerned with the influence of biocides on natural environments, wild life, etc. He sight therefore be expected to have a wider appreciation of the overall problem and of its assessment in terms of the hazard to man. On this latter aspect he was of the opinion that there had been a tendency to overplay the hazard to man of insecticides and PCB's, and that it was very doubtful whether the toxicities of PCB's were greater or similar to those of the Insecticides. Experiments with rainbow trout in water con taining 1 part of DDT in 109 of water had shown that death occurred in six weeks after which the concentration in the fish muscle was 1 in 10. In other words there was a concentration factor of lOOO in 6 weeks: this would take place mainly by absorption in the gills. Ho believed that some similar experiments with Aroclors had been carried out in the Ministry's London laboratory, and phoned for confirmation but was unable to get this during our visit. I am therefore endeavouring to get the answer to this perhaps significant experiment. Mr. Holden's analytical work has been concerned largely with extracts of seals and fish taken in Scottish waters, and he has observed similar peaks to those found by Jensen and the Government Laboratory. Extracts from freshwater and seawater fish show fairly low amounts of PCB's, while seal blubber contains considerably more. Reprints of relevant papers were given to Dr. Keller and there was a discussion on analytical work, much of which was carried cut for other bodies, e.g. the Nature Conservancy. Much of tho work remains unpublished and he saw little chanco of rectifying the situation. B. Yisit to Tunatall Laboratories, Shell Research Ltd., Sittingbourne, Kent. Tuesday, April 29th, 1969. Dr. Mr. Dr . Mr. J. Robinson - Biolc gist A. Richardson - Ann lyst St evonson - In char go of Experimental Anima1 House. De Corsen - Laborat ory Administrator. Dr. R. E. Keller - HC Dr . E. P. Wheeler - MC Dr . D. V.N. Hardy - MCL Shell has naturally been concerned with the problem of insecticidal residues from the outset and the coat of the analytical effort and its interpretation must have been very considerable. To Shell the PCB aspect has been simply one of analytical complication, and although at times there have been suggestions from their commercial people that the focus of TRAN 021766 STLCOPCB4024883 6 toxicologic*1 interest night be transferred from insecticides to PCB's, there has been no attempt to do so. In fact papers by Robinson do not refer to PCB'a but make a very sound approach to the insecticiaos problem and to its true perspective. Nevertheless they had collected some information on possible usage of Aroclorc, for example, they had noted that the Coal Board disposes of 1,000,000 gala, of high pressure lubricant each year. Did this contain Aroclor? We thought it unlikely but questions concerning safety in use of Aroclors had certainly been referred to DCL by the Coal Board and it was therefore likely that some minor uses have been developed. There night conceivably be a small content of Aroclors in the high pressure lubricant. Usage of insecticides was of a high order, and in Kent alone 1000 tons of DDT had been consumed since its intro duction after the 1939-45 war. Reference was also made to usage of Aroclors in cutting oils; the Government Laboratory had suggested that this was a possible source of contamination. Cutting oils are normally sold as proprietary formulations and it would be difficult to estimate how much Aroclor is consumed in this form. Shell would much prefer to have a direct method for estimating insecticides. Now, owing to the stability of PCB's, it was necessary to estimate insecticides and PCB's, then PCB's by destroying or removing the insecticides and getting the insecticides by difference. Aroclor 1254 had been fed to chicken at 10O parts per million Of the diet and no adverse effect observed over a period of 12 months. The Nature Conservancy has carried out feeding tests on Bengalese Finches with DDT and found no adverse effects, and similar results have been with chicken and quail fed on 10 and 20 parts per million of Dieldrin. Other workers found some effect on mallards and chicken. At the Government Laboratory it has been shown that human fat (from mothers' milk) may contain FCB. Reference was also made to the work of Hr. Alabaster, Liniatry of Agriculture, Fisheries and Food, on toxicological levels with fish. It was agreed that many ox the specimens submitted for analysis were not reprosentitiv-j of the total population, e.g. predators were heavily weighted, and of the sick and dead birds, were most frequently collected. There must be large numbers of each predator much less contaminated than those submitted for analysis. Samples of fish oils and margarine (supplied by Unilever) have been examined, and while I-'CB's can be found in the oils, they disappear curing the hardening process so that margarine is free. TRAN 021767 STLCOPCB4024884 8- - I C. Discussions nth Representat1yes of the Government Laboratory at iionsanto House Thursday, May 1st, 1969! Mr . J.C'G. Tatton - Laboratory of the Government Mr . G.B. Collins Chemist t M M tf Dr . R.E. Keller Dr. E.P. Wheeler Dr . D.V.N. Hardy - MC - MC - HCL Mr. Tatton said that the possible danger of Aroclors used as plasticizer (in food packaging and in lacquers for cans) had been considered quite early on and reference is made thereto in the Annual Report of the Government Chemist 1953-4. He will send me a photostat copy. Ab regards residues in wild life peaks not due to pesticides were observed in 1963-4 and this caused trouble in view of the complicating effect on insecticide determination. Attempts to identify the disturbing material failed until Jensen showed ^.their nature. Jensen's work has been fully confirmed and I extended and PCB's have been found in eggs, predatory birds, f rarely in human food, and traces in cod liver oil. Human fat I seems to be free from PCB but there may be 2 - 12 parts/10 of insecticide. Some PCB found in human lung samples. Work has been carried out on air and on circumstantial evidence PCB must be present . 1 part DPT compounda/lO^ parts of air has been found. The analysis in complicated by the presence of hydrocarbons. Tatton will supply references to this work which was carried out on sample of about 1200 litres. The content of insecticides in air and water is variable, generally higher in London due to soot particles acting as absorbent, and also depending on when spraying is in progress. Dr. Kroll (Water Research f- jsoc ia t ion) has failed to find PCB in river waters at parts porlO^. Many sampleo are cent to the Government Laboratory by the Nature Conservancy, but having carried out the analysis nothing more can :a done as the source and significance of the ample are known inly to the Nature Conservancy. The peaks caen in the chromatogram represent only part of those observed in commercial camples of Aroclor 1254. Probably the middle components ore favoured by the analytical procedure: certainly ponkn due :o higher boiling material can be obtained by raising the operating temperature of the column. Recently high PCB figures have been found on herons (several hundred parts per million in the liver), kestrels, owls TRAN 021769 STLCOPCB4024885 Q and kingfishers. Dr. N.W. Moor-j (Monkswood Experimental Station) might be prepared to diccuss their significance and the geographical .'actor. Tattc..: considers that Jensen's peaks are more ir. line with Bayer's Clophen. He thinks that some of the bird ..araples are representative as they were taken from colonies. Tatton alsc referred to possible traces of PCB nature in occasional food samples, e.g. milk, mutton and beef fat. He will supply me with copies oi all relevant papers, including a report on some new detectors for VPC analysis. Dr. Keller will reciprocate by sending chromatographic CUrves for the various Aroclors. I referred to HCL work now starting on the biodegradation of Aroclors and suggested that cur workers should contact him on the analytical techniques. He would be most happy to do so. D. Discussion with Representatives of Cromer & Warner, Consultants, 140 Buckingham Palac* Road, London, S.W.l. Thursday, May 1st, T5F9T Sir Frederick Warner Dr. David Train Cremer & Warner Dr. R.S. Keller Dr. E.?. Wheeler Dr. D.7.N. Hardy HC MC HCL This was a lunch discussion arranged to determine the possible value of this firm of -.onsultanto in the assessment of the PCB problem. Cremer & Earner have conttcctsd with the Port of London Authority (and possibly with others too) to study the effect of certain contaminants in the Thames. They are concerned specifically with detergents and Mr. Cramer is Chairman of the Government Committee which has been advising on the problem due to hard detergents. Cremer k Warner are also advising on atmospheric pollution due to sulphur dioxide and smoke, and on the design end interpretation of data from the recording stations. They have also acted as consultants for the new project in relation to the effluent disposal problem. have advised that the effluent hould be discharged 1 from the shore at a minimum dep.'.h of 75 feet. potash They mile TRAN 021770 STLCOPCB4024886 10 They ire re interested broucly in our problem and fully appreciated that after all the _nalytical work had been done it would be necessary to interpret the data and to correlate it to safety standards in a way ,7hich would carry conviction with the authorities. They seemed confident that this area vii one of their strong suits, cut it is far too early to assess their ability to contribute to /he present problem. D.V.N. HARDY JTTB/HMH 6.5 .69. Footnote (See p.4 - Summary, It_m 3) Compare Jen3en's innings that observed prior to 1944. o contamination was TRAN 021771 STLCOPCB4024887