Document aJR6mQe7gX3Yn5VLgrmgKdbYR

CURRICULUM VMAE Of DAVID WOOD 60000110 NAMEI David Wood ' NATIONALITYt British PLACE OF BIRTH: Stafford, Preat Britain DATE OF HIRTHj August 2. 1939 ADDRESS: Avs Washington Luis 2500, Csss 9 06662 Sao Paulo Brasil EDUCATION: St, Martin's Elementary School, Stanford Grist Britain - 1964 to 1949 Stamford School, Stamford, Gnat Britain - 1949 to 1957 Trinity College, Cambridge University, Cambridge, Crest Britain ** 1957 to 1960, B.A, Honours Chemistry and Parc II Law Tripom PROFESSIONAL ACTIVITIES Assistant Technical Salesman, Engineering Chemicals Croup, Momenta Chemicals Ltd,, London, Creat Britain May 1, 1961 to Juna 30 1966 Salee Supervisor, Dlalactrlc fluids, Monsanto Europe S.A., Brussels, Belgium - July 1, 1966 to October 31, 1966 Product Supervisor, Dielsctric Fluids, Monsanto Europe S.A., Brussels, Belgium - November 1, 1966 to January 6, 1968 Market Supervslor, Food and Fins Chsaicsls, Monsanto Europs S.A., Bruastls, Belgium - January 7, 2968 to January 4, 1972 Produce Manager, Fine Chemicals, Monsanto Europs S.A., Brussals, Belgium - January 5, 1972 to February 20, 1974 International Market Manager, Fluids Functional Products, Monsanto Company, St. Louis, Missouri, U.S.A, February 21, 1974 to March 31, 1975 Markst Manager, Dlalactrlc, MIC Specialty Chemicals, Monsanto Company, St. Louis, Missouri, U.S.A. ~ April 1, 1975 to December 31, 1975 Industry Manager, Dielectric, MIC Specialty Chemicals, Monsanto Company, St. 1-oui*. Missouri, U.S.A. ~ January 1, 1976 to December 31, 1977 i PLAINTIFF'S i EXHIBIT /.z.z HARTOLDMONOO11052 Curriculum Vitae of David Wood 60000111 P*l 2 LAST JOB ACTUAL JGS Market Manager, Heat Transfer and Process Chaoicala, MIC Spacialcy Chemlals, Monsanto Company, St. Louis, Missouri, U.S.A. - January 1, 1978 to December 37, 1979 -Manager, Raw Materials Purchases, KM&H, Corporate Purchasing, Monsanto company, Sc. Louis, Missouri, U.S.A. - January 1, 1980 to April 30, 1982 Director, Chemicals .4 Plastics, Industries Monsanto S.A., Sao Paulo, Brazil - May 1, 1982 HARTOLDMONOO11053 cc: Mr. D.S. .raeron - ME RISING & STRAND OP/BO AKTIESOLAG TTLCrOM I )lfl| II roiTomor rrUOHAM I MCHMIS TTLXXi I 24 * tAMKOIROi 7J.OJ4* 28NovemberSTOCKHOLM V* SVCAVAOCM 4 7 , lh66 Monsanto Europe BRUSSELS 5 Belgium Eor the attention of Mr. D. WOOD Dear David, re: AROCLORS --^ As mentioned, there has been some publicity in Sweden./ concerning investigations made at the InstitutionAnalytical Chemistry at the Stockholm University. These have revealed that a group of products called Polychlorinated Bi-Phenols - PCB for short - accumulated in certain organs of animals. They are said to be related to DDT and equally poisonuous. The findings were discussed at a meeting of scientists at the Wenner-Gren Centre in Stockholm on November 22. Below please find a translation of an article in the Swedish dally paper "Dagens Nyheter":- "It is found in salmon and in pike. It is found in sea eagle living on fish. It is found.'.bn thw-.^sur face of the needles of the fir trees, that is the air. It is found in the hair of -a five months baby... '" ...... .................................. .................................... .............................. ......................................................... ....... \'' '. ......... j >i .. . The scientists working with biocides have for ailong time seen this something as unknowq. "peeks',' on ytheir gas chromatographs and at a meetlngs-q.t the Wenner- Gren Center, Research Assistant SSren Jensen of the Institution for Analytical Chemistry at the Stock holm University could reveal the identity of these peeks. It has been found that they consist of a group of poisons, Polychlorinated Biphenols (for short PCB) which are closely related to, and equally poisonous as, DDT. PCB is broken down considerably slower than DDT and gives rise to damag^of liver and skin. PCB is no COMPANY iran CONFIDENTIAL 056^61 HARTOLDMONOO11054 if i :* i !< c *. b t r a o P- * f * t 4 MESA, Brussels Mr. D. Wood 2. used as & herbicide. it is not manufactured in Sweden but is supposed to used by the'industry to quite Borne extent. No speoial industry can so far be acouaod of being the source of contamination. Research Asst. S. Jensen has tested 200 fishes and a number of birds. He has taken several samples of air and has reached the conclusion that PCB is equally oonanon in Nature as chlorinated hydrocarbons of the type of DDT, D^H, and Lindane. Even fish in Laddjojaure in Lapland contain PCB. Mr. Jensen has also found that PCB doeB not appear in animalB living on a vegetarian diet, such as the elk. In the course of his work, Mr. Jensen has not found anything indicating that the aource of contamina tion oomea from agricultural additives. It is, however, obvious already now that PCB is moat frequently found in organisms living in water or feeding from water animals. In all examined pikeB PCB was found. In a sea eagle found dead outside Stockholm it was found that the liver contained 30 mg of meroury per kilo, 76 mg DDT and consider ably more PCB. The exaot figure has not yet been determined. PCB is found in water and in air, and not only in the Swedish air, but also in e.g. London air. Mr. Jensen has not yet been in London for sampling but could identify the poison by studying a gas chromatogram of air published in a British techni cal Journal. Mr. Jensen har also examined thebalr of his family and himself and has found PCB on all samples. Most PCB was found in the hair of his wife but most sensational was that the girl aged 5 month;, had more PCB in her hair than her brothers and -slaters of 3 and 6 years. Probably the girl had got the poison via the mother's milk. ....... In th9 State Museum Mr. Jensen has examined the whole collection of sea eagles dating back to l880. Ey testing it could be established tnat PCB was present only in birds from 1944 and thereafter while birds colleoted before 1944 were quite free from PCB. QQMPThe use of PCB in Sweden is not estciblished in detail. . 11-- ir^CKiT!At According to American sources these types of products QQ^lr lUtCiN I If* are used in the manufacture of a variety of heat- resistant materials. They are used for electrical insulation, for fire-proof heat transport in ^ hydraulic oils, in lubricating oils used at high JRAN 0 5 6 *6 2 HARTOLDMONOO11055 I N t. * STRANO ISA, Brussels - Mr. D. Woo 3- temperature..and pressure, in paints and as pig-.... ments in various plastics. PCB is not imported only as such. It is also part of several finished products. Nothing is known as to the way in which it reaches the water and the air. According to Mr. Jensen, products containing PCB should have this openly declared. PCB is equally harmful whether absorbed via the skin, through the food, or by inhalation. In con tact with the skin it can cause ae dema. For DDT the highest permlaslble concentration in the air has been set at 0.5 - 1 mg/cu.metre. For PCB it has been mentioned to be 0.5 mg/cu.metre. Mr. Jensen will now try to get more complete analytical material. He hopes eventually to be able to disclose the source of the contamination and will also Increase his cooperation with toxocologlsts and geneologlsts." Another daily paper, Svenska Dagbladet, has a similar article. Here it is mentioned that Mr. Jensen, work ing under Laborator (Professor) Gunnar Wldmark, has disclosed facts which will have far-reaching Importance since the findings have proved a new source of pollu tion of the nature. One of the participants at the meeting was Dr. A.V. Holden of Scotland, scientific contact man between the twelve O.E.C.D. countries, who has established coordinated analysis of chemicals used and found in nature. I suppose there is no doubt that what has been termed Polychlorinated Biphenyls is equal to Aroclor. There is also no doubt that the published facts will cause considerable unrest in several quarters. We probably will have to have Aroclor registered with the Swedish...... Board of Poisonous Substances and the industry will have to' be particularly careful in handling the material. The problem in some cases of course may be the disposal of used material. I understand that there hardly exists a convenient method of destroying Aroclor and that possibly burying unuseable material may be the only answer. We shall be glad to hoar from you soon. Yours sincerely IRAN 056463 COMPANY RISING & STHApJb . -odi-AG HARTOLDMONOO11056 Brussels, Belgian ; JLnfc Decsariber, IBM ;; : ' , Aroclpr gwodsm . X. JLtpino - Brnsseh Dr. Iwt fcUy - ft. Louis Barely - London ."SiHis C0PXI^X*<A. gtaenrod - *t. tools ^ - .B* Buchanan V t. Louis .. Bear daosrps. - ; - . ;. . X attacha oopy Of a letter received frost Ola Palm in Stockholm. ... X b&ve sent oopiea of this letter also to the appropriate departments ; .. . ' within oar Own organisation. Xn consideration of ths inportanc* ' " tr* an* placing on davelopnant .of the Bwedish market for hroclmr oner the next five years, wo would ha grateful if you oould arrange for this information to ho considered by tha appropriate departments * in ft. Ionia and their c'cissisnts transmitted to as as soon as possible. ' *' \V ~` -VBaBod os- the recommendations ends by car nodical departments vedhall - bare tc. docIda whether to arrange for publication of data in Sweden r Mfc. ' V- t . i * . ' ' .. Xn relation to tie specific problem meationed of disposal of used mntexiaie, wn wonld be interested to learn how this problem la hmniied in Smart rra. Zn the 9.X. many coi^anies hare been burying .mat# Lai in dross* material in the drams having beam absorbed into vm -cnlite or some similar pomous notorial. Baa any entirely safe method been developed for the disposal of wasteAroelor ? . &.B* . jfhiaiking of tha total gpsaati&i&s of Azodor used in Sweden 7^-:ooepa^ ad' %yith the week larger oolune* of Peotachlorophsaol and Boditsa . .IHftatachloxtipbsnafe*, for water treatment in the paper industry and .' saaetaln control In the tia&r industry. If it likely that the .. chlorineted, phenols show slllar dhzonatograpfcie traces to tbe ctlorlyts^i bl-phaaolsX , ... ' ' .% , V * EXH,Bn'N0^7^j STR 017390 HARTOLDMONOO11057 It. Louis December 12, 19(6 AROCLOR SWEDEN Hr. D. Wood BRUSSELS / o*< -- />o A. Arpino - BRUSSELS c=:^ --O* ** Buchanan - CBOCH . . D. V.M. Hardy - LONDON -....-.......------------R. A. fltoonrod-----RSTBE............ Z do not beliave that v can glibly accapt Axoclora aa a synonym for polychlorinated phenols that vara disoussad at the mating of scientists at the Wanner-Oran Centra in Stockholm on November 27* There are polychlorinated phenols which presumably could induce derivatives from, or impurities in pentachlorophenol and, especially, 2,4-D and 2,4,5-T. These compounds would be much more liable to appear in salmon, pike, and sea eagles than any derivad from Aroolors. There are many chlorinated polyphenyls that can be formed during the manufacture of 2,4,5-T end probably pentachlorophenol, e well. Our only problem is whether or not we want to bring these facte up and have our herbicide program receive another black eye. This, Z will have to leave to your judgment. Z think the question here is primarily an analytical problam. How can we find out what product Nr. Jensen is talking about? Can we compare these chrometographic peeks that Mr. Jensen is describing with anything found in Aroolors, pentachlorophenol, 2,4,5-T, etc? Z admit I am out of my depth here but Z think another ooopound is indicted rather than Aroclor. MEX/ln R. Emmet Kelly, M. D. TRAN 056624 r m- HARTOLDMONOO11058 oi: "To* ic ity/ NOTES ON THE NEWS continued <-tniriT. ,y>eC /fU potatoes in one operation. Work is also in and Itss detected PCI) fir.->t in nil Cliglr Irmi progress on a double-row harvester. 1944. That tractor wheels arc indeed harmful In Swcdon. PCB is known m be used ji to soil hits emerged from a unique field elrciriral insulations, hydraulir ml- study at the institute. Using a gamma-ray high-lcmpcraitirc ond lngh-pre-sur. probe and detector, researchers there hove lubricating oils, paints, bieipicrs aw been able to observe for the first lime the varnishes, and as pigments in varimi actual local profiles of soil density across plasties. It docs not seem tu In: u-cd ie>. tractor ruts, plough furrows and the like. insecticide. It is hoi destroyed by iiirmera They have related these to the failure of tion and mnv enter the body direril plants such as raspberry canes to grow through the skin, by breathing, nr bywa where the soil has become compacted. of food (especially fish). It is pnrlinil.tr Clods are also typically the result of the harmful to the liver, and also the skit passage of heavy machinery across the soil this has been demonstrated by rxprr for various purposes such as hoeing. At so that cutting down the extent to which mcnls on mice. PCII is ninrh harder i ihr Notional ]nlitutc of Agricultural tractors and wneeled vehicles run over the break down than DDT and ibrrr is rvr- Engineering, Ilowden, Midlothian, tome soil will undoubtedly improve production. reason to suppose that il is rnurh mm interesting new attitudci are developing, This is by no means the only application difficult to get it out of the system. Tl however. For one thing herbicide! have of modem methods of science to farm substance has also been detected in c lie a eliminated the need for close manual mechanization at N1AE. Novel work under procedures which means that it is no way r.inis at automated tingling of sugar longer necessary to grow all crops in single beets. Again it is herbicides like paraquat rows. There would be distinct advantages that have made such advances possible. in growing potatoes, for instance, in beds Manual thinning by hoe is tedious and as wide os three or four rows. It would be expensive. The plan is to use a machine more economical of land, earthing-up equipped with photoelectric detectors e.uuhl be done quicker, and the soil would sensitive to the spectral absorption lines suffer less from the compressions! of the green chlorophyll pigment in leaves. damnge done by aprieult'j*-al machinery. Signals from this device, indicating the. There is a drawback, however. Tradi . density of foliage, will control paraquat tional tractor design docs not permit the spray which will squirt the excess plants, use of wide strips; and no one elsewhere leaving only those required at specified serins to have given much thought to ways intervals for optimum growth. in which troctors could be improved. At ~ Engineering data during field trials on NIAK engineers have had a hard look at new equipment is about to be collected by over London and Hamburg and also ' seals caught ofTScotland. It can tlirrcfm be presumed to be widespread lliruugiin the world. LOAVES AND FISHES The famine which now threatens parts India has tended to focus the attention the developed countries on that su continent's chronic inability to feed teeming people, but a wurumg note ran last week from another less publiciK what formers are going to need in the future and have designed an impressive "self-propelled, multi-purpose toolframe", radio telemetry, and modern dataprocessing methods are under develop ment at NIAE.` area. Dr B. R. Sen the Indian Dirrrt Central of the UN Fnntl anti Agricultu Organization was addressing t regini which could well come to dominate our conference at Punts del Estr, Urugm rural landscapes in a few years' time. He lambasted the governments of l-v Essentially it consists of a large box frame, REPORT OF A NEW supported at chest-height on conventional tractor wheels--a large pair at the front . CHEMICAL HAZARD America for their unwillingness tn fn wlial could be "a very serious siiunn indeed", ll would lake, lie said, an inrre; and small pair at the rear corners. At the A Swedish research worker has expressed in food production of four per rein a vi front of the frame in the centre is a power concern over the increased amounts of to stem "social and political unrest \th ful, 70-horsepower tractor engine coupled polychlorinated biphenyl (PCB) entering still prevails", or even to prevent it fn to the. driving wheels by independent oil- the air, presumably from industrial smoke worsening. driven Itvdrodynomic motors. and rubbish-dump smoke, and being Dr Sen's warning comes none ton so The driver sits high up on the rear absorbed by water and taken up by fish Malnutrition if not artual hunger is wi member of t he box frame in a teat that can and later humans. PCB which is related spread in Latin America, where prr-en| be hydraulically shifted from side to side, tn and as poisonous as DDT was detected food production lias dropped In four or turned right round to face the reverse by Mr Soren Jensen of the institute for cent in the past six years. At the -nmc t direction. He has two levers at his left Analytical Chemistry,. University of the population is expected to double it hand: both"forward gives a range of ' Stockholm, in some 200 pike taken from (to 422 million) by 19R5. Dr Srnhrlie forward speeds; both backward, reverse different parts of Sweden, fish and fish- the four-pcr-ccnt rise to be lerlinir speeds. By moving them independently spawn throughout the country, an eagle feasible, if an all-out effort is ninilr ii the wheels will revolve at different rates which was found dead in the Stockholm Apart from the struggle In inrre and assist turning. The rear wheels are Archipelago, and in his own. his wife's food supplies to keep pace with pupulai telescopically mounted and can be raised and his baby daughter's hair. As the baby however, efTorts arc also bring niaih or lowered hydraulically. They are self is only five months old her father con overcome tradiiionul prejudir.-s aga levelling over uneven ground. Agricultural cludes that she got her dose of PCB with, various foods which may In- pirn .implements are mnunted--without the her mother's milk. though neglected. need for soil-damaging wheels--in the It is not known at present how much In the waleri of Lake Vi.-tnrin. ecntrr of the box frame. Implements, of this substance is dangerous or even instance.--they cover on area nbnui likewise, can be designed for hydraulic fatal. If it is comparable with DDT llipn the size of Ireland--there ore v* i kliDN operation and the frame is equipped with limit would be 0.5 mg per cuhir metre of tilapia, a firm while fish, weighing at two large oil tanks at eacli front corner air--and, for comparison, the desd eagle 8 oz and very tasty.' European firms I and srvcral hydraulic take-off valves. had at least 10 times as high a concentra already asked the Tanzanian pmrrm The whole contrivance is simplicity itself tion in its body. For purposes of elimina shout the possibilities of sending fn to control. tion Mr Jensen has obtained feathers from fillets to Europe hut the local prop!, A planting unit has now been construc eagles preserved at the Swedish National by no means as keen to cal this so ted that will plant and ridge four rows of Museum of Natural History since 1BB0 fare. TRAN 056625 HARTOLDMONOO11059 INSTITUTE OF ANALYTICAL CHEMISTRY university or Stockholm Ra*Uf*rl< W, StoeUwIm M. SvmUb 0e Stockholm, December 29, 1966 ....Mr* Ford......-......... ......--..... Monsanto Chemioal Oo 'BOO Lindbergh Road ' Bit Louis, Missouri 63177 * USA Last year 1 had the great pleasure of visiting you at the Monsanto Co In St.Louls to discuss analytical problems of the phenolic composition of TCP* We were later kindly supported with samples by Mr. J.S* Thomas and Ur* A.?, TJelner. Our analytical Investigations are almost finished and we will send you a reprint of the report when they will be available* This letter Is to inform you that we recently have identified most of the unknown CC-peako at residue analysis of pesticides in biological samples* By the aid of combined GO and mass spectrometfy-Mr* Jensen of t this Institute has found the unknowns to .be polychlorinated biphenyls which among other companies: are manufactured by Monsanto, trade name Aroclor. Added to this letter you will find a preprint of the synopsis of our publication which will appear In Acta Chem* Scand. (Bummer 1967)* Two gas chromatograms are also added to show that the chlorinated biphenyls are enriohed In ecological series* - In the sample of the sea eagle were found! Polychlorinated biphenyls BO ppm} ordinary chlorinated pesticides BO ppm and merpury) 40 ppm* At present we have no knowledge of the biological significance of the presence of these oompounds In llvlhg organisms* .We have started a collaboration with the Dept, of Toxicology at the Carolin Institute but we should Very much appreciate to work with your toxicologists - ' over this problem. .' . We will be glad to give you any further informations of the results . obtained in this laboratory* - 1 1 1iI Sincerely T ours l< I { P/f - ' Gunnar Vidmark v- U EXHIBIT NOA2Z , . t 1 1 "AAr An ' V: TRAN 056035 HARTOLDMONOO11060 lJTth January, 1967 Aroclor - Sweden BVNH/aBV... .... ........ 10 P.G. Benignus, St. Louis C. R. Buchanan, St. Louis . D. S. Cameron, Brussels Hr* R. Etamet Kelly, St. Lcruie G.E* Graham, New York R.A. Steenrod, St. LouIb . B. Wood, Brussels J.A. Evans, London R.A. Baxter, Ruabon 'JAN 16 1967. On 2nd January 1967 Nr. A. Richardson of Shell Chemicals' Tuns tall Laboratory, Sittingboume, Kent talked with me over the telephone concerning the Swedish Press report relating to the identification of "Polyclilorlnated Biphenols" as traoe contaminant in sea birds, fish etc. Richardson has been working for some years on the similar problem with insecticides such as BDT, vliich are known to have wide distribution in traoe quantities. He had already found that the chlorine-oontaining residue contained Bubstances more stable than BBT. and just as SBren Jensen reports he has obtained spectrographic evidence that these axe very similar if not identical with Aroclors. He has obtained samples of Aroolors 1242, 1254, 1262 and 54&0 from us,' and would now like to have small samples of any chemically pure Aroclor constituents which ve may be able to supply. Milligram quantities would suffice for his puxpoce. Mr. Richardson was quite sure that the compounds reported to be "polychlorinated biphenols" are really meant to be polychlorina'ed bjphenvlb and as support he has sent me a copy of the synopsis of a paper entitled "Pesticide Analysis* Presence of Polychlorinated BiphenylB at Residue Analysis of Biological Samples" by Sflren Jensen and Gunner Vidmark (photooopy attached). I discussed with Richardson the soundness of Jenserfs claims, and was assured that his work and findings axe sound. Jensen is on the staff of the Institute of Analytical Bhemiatiy, University of Stockholm. A note on the staff and work of the Institute is attached. From this you will see that Jensen is wholly concerned with the analysis of chlorinated pesticides and with the work of stations for routine analysis. I would he glad if Br. Baxter and Ur. Buchanan would arrange to send me milligram samples of any pure Aroolor constituents that may be available at Ruabon and St. I^ouis respectively. COMPANY CONFIDENTIAL TRAN 007566 HARTOLDMONOO11061 IVftOFl t.A. #* # , ny* . # <AM 4 j ' MTI t' i MSJWT . l O Brussels, Belgium 26th January, 1967 SWEDEN, AROCLOR niniwm i DWtgb 00 p* P^nrgnus - St^ Louis D. 8/ Cameron -^-BirusBels Dy D- V/ N; - London Dr. R. Qrmjp<^Kelly - st. Louis R.A. Steenrod - st. Louis TO..........:.... ...O. R. Buchanan - St i ; : M'i i ' Louis We recently sent you a translation of a Swedish newspaper article referring to the identification in nature of polychlorinated biphenols. Because some of the uses claimed for the materials fell in line with the uses of our own chlorinated diphenyls, we made a point, during our recent visit,to Sweden, of visiting the research institute involved and discussing their particular programme of work. To eliminate any earlier confusion that there may have been, I~~Bhould like to emphasise that there is no dou'Ht~~,Haf'The chemical which is the subject of the investigation wnd~tha news release, is chlorinated diphenyl l.e.~Aroclor. ' The company that supplied the mass spectrometer which was used in the research programme, in fact have recently put out a press release on this work. Although X am horrified by some of the headlines in this press release, it does basically describe the research programme carried out in Sweden, and describes in clear terms, how chlorinated diphenyls were identified. I therefore, enclose a copy for your files. ! Jensens only aim in life as an analytical chemist, was to identify ; [ .. the substances found in his research work on the occurrence j;1 ' of insecticides in nature. The unfortunate'aspect of the ['| j ' i' ; . situation is the comments which have been added to Jensens work, ' . He showed what was present and unqualified people have made :;l" statements as to the possible effect of what he has found. 'ill . .j . : U I*- ' | . ; Summarising the publication position, there were original articles ; I'j; i ] r ; covering the Stockholm conference in the Swedish daily press, - i'| : and these reports were picked up also by the Danish press. You l-.i 1 | r ; will have seen from D.V.H. Hardy's memo of the. 12tn January I' that it has also been picked up by the Shell Chemicals Laboratory i '\ i' in Kent, U.K. Jensen also divulged that he had been contacted , I | 1 1 i. by the Swedish American press agency who intended to include . . " i information about this research work in their monthly review "The Swedish American Journal". There ia additionally the . . press review issued by LKB Produetor AB which X imagine to s( have i been sent to.a number . of technical journals. j mm-mmmiml f < (t r' i1'.. ' I f?/-f - &Jood 1 EXHIBIT ( . 7 RAH 08594? . .../... HARTOLDMONOO11062 o 0. R. Buchanan St. Louis )' -2- 26th January, 1967 . }. I }' j ' , \\ ` . , > i1:? ... . t, v'.i !:. . ;l i -i i. :> i i:! I H'l'; il i :;iv! IiI . ' < I. * ', :i i ' i , ..jhi Effect in Sweden This matter was raised with us by every capacitor manufacturer in Sweden that we visited. Fortunately there has not been too much adverse comment as yet from plant workers since they have not associated the polychlorinated biphenols mentioned in the article with Aroclor or Pyralene used in the Swedish factories. Jensen, however, stated that he had been approached pegresoonnaaully by--fl6Veral workexjaTjiBap.afata.d_wi"th~~chl or-Lnatod c^jiIpphheerrnyyIllsfo r non-electrical uses and these workers were quite wroorrrritBedtrnas to the possible e3 ` " ^Future Research Arrangements are being made in Sweden for this work to be taken over by one of the medical institutes who hope to Btudy the toxicology of the poloychlorinated diphenyl residues at the levels of concentration found by JenBen. Additionally ' a geographical survey is to be carried out to try and determine where the highest concentrations of residue are appearing and, if possible, to detect from this the method of escape so that more security precautions can be taken. We were asked by Jensen if it was possible for Monsanto to supply any samples of the pure isomers of chlorinated diphenyl since his work indicated at the moment that the lower chlorinated isomers are fairly easily metabolised, and the potentially more dangerous constituents are the more highly chlorinated members. If he can get hold of pure isomers, ha would like to carry out some work on comparitive rates of metaboliBation. Jensen is forwarding me copies of his mass spectrographs and details of sample preparation so that we have all the details i of his research work. ,\ r *;: .* 1 The point that I have made to Jensen is the need for care in any further publication of his work which is made. He accepts ' that the toxicology of chlorinated diphenyls should only be discussed with detailed information about exposure concentrations . and exposure times and that generalised statements out of ; context can only arouse undue public, concern. If any technical journal takes up the press release from the LKB Productor Company, there is little that Monsanto could, or should do, in the way ' of publishing rebuttals. We do not want, personally as Monsanto ` to get too involved in this question. X am hopeful that we 1 j TRAN 0359*8 A * HARTOLDMONOO11063 o O' il . . ;i* i* '!< < i; i. jj i;. ' . i*: ,' , .1 , ,* i ' i< :i ... \ i' ; . !! ; >v * i 'ii1 ; 1.:*. - '*1<I v)' *: i ii .1J ; , i "i!; O. R. Buchanan St. Louis - 3- 26th January, 1967 might persuade Jensen himself to write a letter defining the true extent of hi* own research work and placing hi* , result* in their proper perspective. It would certainly he helpful in gaining his further support if we were able to make available to him any small quantities of pure isomers. Since we are not alone in supplying polychlorinated diphenyl* to the Scandinavian market, I have drawn this matter to the attention of the other askarel manufacturers in Europe. ' i 'r I !* I . i^ j *: A* you will see from the press release one of the major point* that is made is the difficulty in disposing of ^aste chlorinated diphenyls and again 1 must mention that constructive recommendations for the safe disposal of our materials would be most helpful. , ; ; .. .I ji; I i i; * i' *''* . ,. f 1. . . *J* . f. i * .1 *' :i i.T; W >. ' t 'i-fr-s i * /, . \`MA V.- >! . < ! i: .t 7f. -tW V::.- i ;> r: .. : ; M. :;T :.:0; Utf+T-X*-; :!: '> O::!- .v'1: .* / = I..': ; *-,:* . rO*:rOv/ 4* n . *1 . . * ' ' 1. . t '; ; * ' * . 'Ii*/V * *\. *4*. 1 ' ` . I ; r- < i... r *. ***'> * , 065' HARTOLDMONOO11064 } . ................. _ Hot Tor release until January 20, 19$7 i ..... ............. ......... ..........' ' ' . ;! rOlOOH! - LKB HELPS TO HAKE A SAFER VORID . i.i " ' ' - 1 -- ' ' *1 .Guedish fire produces instrument that detects a previously unobserved poison in rih .1 ( ' "" ' " "" * ' fowl, and mammal . 1 The b'ature of the Poison i;i;jThe poison that has been isolated is a hitherto unobserved chlorinated hydrocarbon ..j having eight chlorines in the molecule* This polychlorinated biphenyl (PCB) wee 'jisolated in residue analyeis carried out with the LKB Combined Oaa Chromatograph*' '^Maia Spectrometer, LKB 9000. iM'.jlOO/W of residue from 20 mg of fet, taken from a Sea Eagle found dead in the Stockholm ''hi I archipelago, was used in the analysis which vat made by Sflren Jensen, of the Ins -itute jof Analytical Chemistry of the Univereity of Stockholm, who hat been engaged on this 'type of research for tome considerable time. The dramatic importance of thia discovery lean best be understood by studying the main characteristics of PCB; Si Very high stability. Capable of being boiled with nitric acid without destruction. { 2. Has hardly any metabolism in living organisms. Can have a steady build-up in the ' human body and traces have been found in both adults and children. 3. If more than four chlorinea are present PCB is non-inflammable. :! As well as isolating a poison this research has drawn attention to tha need for dote lit co-operation in two parallel -lines of investigation. The study of the persistency and toxic affects of herbicides, peaticides and relatad chemicals, which for acne time now has caused general concern throughout the world, and the quest for improved methods of assessing the pollution of industrial waste. . Ho* the Substance was Identified i {, Initit al research seemed to indica. te that this, than unknown, poiaon oecured as a re suit of the use of insecticides! the usual organochlorinee present in insecticide research were detected pp^-DDT, pp^-DOK and pp^-TDE and certain unknown compounds i , *' : . TRAN 085950 HARTOLDMONOO11065 were thought to be metabolites of the inaectieidea The location of the poisons in . rihf in birds and on pine needles appeared to strengthen this theory. Further inveati`i.;i gaticxis hovuver, inrlv'ing electron capture techniques, gave indications that this Ii , i; supposition vas incorrect. ' - i i \ * ~. It was, at this stage,-decided to use the UCB 9000 Combined Raa Chromatograph-Ha** Spectrometer to obtain aore definita knowledge of the chemical nature of the*e un known compound*, their molecular weight, and number of chlorines for instance, as this ;van known to be the only method currently available which could give the highest degree of poaitive identification. Analyst*, had so far produced a chromatogram from which it |was possible to estimate that tha Cagle sample, previously mentioned, contained DDT and DDE in extractable fat at a con.-entration up terI3 g per kg} .. d the unknown com- pounds in more or leas the sea*' quantities. Many of retsntion times however were not in agreement with those for any known pesticides and a high proportion of unknown | .peaks were present. The purified sample from the Sea Eagle was injected on the LKB '9000 and the mass spectrograms which were i.la: nod of the unknown pen!-*, ah.vjfl the-, r naes 'numbers to be as follows! b26, j>2, 358 end 32b- The molecular difference in each case being 3*1 mass units thereby shewing a family relationship between the unknowns M Chlorine exists as a mixture of two iaotopea with atomic weights 3? and 37 in proper-^ -tions of 75:25. If the molecule hasone chlorine, two peaks will be obtained, one for I Cl^ end one for Cl^y- If there aretwo chlorines it ia possible to have one peak with only CI35, one with both Cl^ and Cl^ and one with two Cl^ and ao on, so the rela tionship between the peaks on the mass spectrogram were found to be: Molecular veight: 32* - 358. 392 *2$ ' Chlorine content; 5' 8* ' T.** 8 * * ' . Having obtained this information it wax possible to calculate the molecular veight of the parent hydrocarbon (FHC) and this was found to be 15b, The most probable formula :for a compound having carbon and hydrogen and giving tha molecular veight of 15b is C12,,10 and thiB can o1* *tiafied vhen the parent hydrocarbon is biphenyl and the unknown polychlorinated biphenyl/ ) .I i*1 ;* i - ......... Once thia fact had been established an approach to industry elicited the answer that PCB was fairly extensively used, and when a sample was obtained and run through the MB Combined Oaa Chromatograph - Mass Spectrometer it vas found that the gas chromato graph gave the tame retention time for both the Eagle sample and tha industrial sample, and tha mass spectrometer gave exactly matching peaks, thus providing absolute verifi cation of the previous analyses. . TRAN 085951 To cross check on. the results and to more fully evaluate their significance, the fes * atuTTed Bea Eagle (circa 1680), from a Stockholm murnw. we re eln *w\?- HARTOLDMONOO11066 . wso u poxson o any kind Vaa discovered. ,.Wms continued i r (J --v * 3- . J This research i . vlth other dated specimens and the first trace of DDT and its metabolized DDf vaa discovered in a specimen circa 19k8/k9 and FCB in 19k2< j : It ha* beer* mentioned tarUcr that traces of PCB were found on pine needlee which . j 1 teemed to indicate wind-blown insecticide, but this is undoubtedly due to the fact j ' that where PCB has kOi or more chlorinee it is not consumed when industrial vast* [' is burnt but is thrown out in the smoke and air-borne over considerable distances. > The effect of this poison on man i not yet fully known. In 1936 tests showed that | P3 out of 2k men employed in manufacturing PCB suffered from an acne, which appear- od 6 to 8 montha after handling the substance, and ir. 1933 it war rcopon- ! sible for the death of three young workers. Tests so far carried out on animals indicate that in all cases the liver degenerates and that generally the skin and thw liver are the parts of the body suaceptable to the poison. \ | J Cu--rrent R e searchii *. . t }. Jefferies and Walker of the Monks Wood Experimental Station in England have rncent- | [j . ly carried out experiments to determine the survival and reproduction of Bengalese j .i Pinches and have found a high proportion contain organochlorines. They are investi- I., gating the possibility of using the residue content of the liver as an indicator ] i; , : of'the dose consumed. ' I Simmons and Tatton of the Laboratory of the Government Chemist, London, England iI . ' | have investigated organochlorine residues in human gallstones and have found them | present in 28 patients from 2 hospitals* I. 1( , 4.. ; These two lines of investigation have been concerned with insecticide and pesti cides but they do serve to show the wide field in which traces of organochloti. occur. ' :.| Some twelve O.K.C.D.nations, among whom are the Scandinavian countries, U.S.A., Great ' i Britain, Prance and Holland are co-operating in research into the prevalence of tftia j' 1 virulent and dangerous substance. ; ,, ` ! LAB . IKB-Produkter AB is fully sensible of the dedication of the scientists taking part in this work in which it has bad the honour and privelege to play an important role by providing an instrument,'the UCB 9000 Combined Gas Chromatograph*Mass Srert v- wter, to give them their first break-through by providing positive identification or PCB. . i " i TRAN 085952 " Publicity Department ' m P t ** + f* < *. HARTOLDMONOO11067 085953 HARTOLDMONOO11068 / .I Q (P ~ C(Joid IEXHIBIT Ur Chairman, ladios and gontlomon. " * < i C In honor to our Brittlsh fcoet I will try to hold this lecturo in AEongthliosht. ltlo of this locture statos, I am today going to toll about tho diocoYory of Bono hlthorto unobservod chlorinated hydrocorbono having up to eight chlorlno in tho nolooulo and found in reoiduo ana- lyoio. Tha chonlonl none of polychlorinated bifeaylB ( In tho following callod PCB). To got fcniliar with PCB I will start with tho chemistry and .toxioologi. .0 flhomistrv 3 I l The main-characteristic of PCB is 1. Their very high stability. Ab an oxmplo they can be boiled with nitrin acid without being destroyed. 2. They aro Ijardly motabolinad in living organism. 3. if more than 4 chlorine are^pre^Bent they are non lnflamable* It is cloar that theee threo characteristics dooB it eaoy to understand that whon they havo entorod the giving organism.- the will have a low persistence . But it in difficult to explain how they find their way into the living organieu. Ono thing seems to be clear, they don't come from agricultural use, but from a technical one and most probable it domes to the nature Yia waetoe that aro tried to bo burnt up, beoause then we have them at .onco in tho air, beoauae of thoir non inflamability. . . TRAN 0 5 6 0 3 6 .Toxicologj . . ............................. - '. / Tho PCB woro introduced in 1929 hod ao early as 1936 Jones and Alden ..- reported that 23 out of 24 men employed in manufacturing of PCB eufferod from ah acno form oruption of the skin. Acne did not appear until 6 to B months after the material was first usod. In 1937 Drinker reported that rata expooed to chlorinated biphenylb in concentration of appfoxi- mately 1 mg/m^ for 16 hours a day for 6 weeks chowdd damage of tho livor. After that time tho allowod 'concentration of PCB in air is.0,5 mg/n^. (?or DDt the same value is 0.5 -- 1 mg/m^). Tho nano authors finished thoir experimente in 1938, and related that those compounds have cn injouriouo effoct, manifeoted solely in the liver. Chlorinated bipohnylol ? appeared to.be the.moot injouriouo chlorinated compounds of all tested. [ * . I HARTOLDMONOO11069 Girecnburg, Mayer and Smith 1939 reported that PCB and polychlorlnetcd naphtalcnos are blamed for the death of three young workers, and that""" pregnant women and persona who have at tmy time had any liyor diseaBoa nro particularly BUBpectible. . ........................................... ............................................ T7odol, Hallor and Benton gave 1942 animals PCB including adminiotration by inhalation, ingootion and elcin abeorbtion. Histological examination of tho Yiacora showed important toxic effect only in tho akin and liver, and tho dogonoration effects in the liver are ODBentially the cone what- ovor was'tho method for ths administration, Paribok (1955/ found ae on occupational poison in the eleotrical industry, mixed "totra and ponta chlorobiphenyl cauoos folliculitis, comodo, pyodermia and other okin affootions, and that its principal toxic effect is fatty degeneration of the liver. ' Miller (1944) injected 69 mg PCB (4 and 5 chlorine) eubcontoneouoly in 32 guinea pigB. Eight to ten days after injection, fat droplctB wero noted in tho liver colls, and after 16 dayB they were present in modcrato or very largo numbers. Rabbits and rats were also tested in this invooti- *>f > gation, as well ao the PCB was adminiBtated both continouBly, eubcuntin- ously or ingested in the food. In the feeding experiment 0 guinea pigs received 2'doses of 69 mg of the chlorinated biphenyl 1 week apart. Leath occurred in 11 to 29 days. Pinally Me Laughlin 1964 reported a method to test the chemical toxicity and teratogenic effect by injection into the yolk sac of fertile eggs prior to incubation. PCB was found between the eight compounds among 100 teoted having tho highest order of toxicity. Ho hatch was found at a level of 25 mg pn egg. At a level of ]0 mg per egg, one chick hatched out of 20 Injected eggs, but died 2 days later. Some embryos which were examined after they died, showed weak deformities (often a short upper brok) and growth retardation. Lead acetate resulted as an example in no hatch at a level of 1 mg per egg. Autopsy of the dead embyos have showed exton 8ive brain damage. Mercuric chloride showed no hatch even at a level of . 0,5 mg por egg. TRAN 0 5 6 0 3 7 As the analytical chemistry is a pronounced service science I have boen in contact with many scientists from other fields during the work with residue analysis, and I have always found this contact -very stimulating for my cwn work. This co-operation often demands that wo ere talking the same scientific language. Because of this need I will today try to give a lecture in low level analytical chemistry for biologists,- illustrated by the residue anolyeio of polychlorinated biphenyls. The lecture will be divided in the following three eub-diviBione: HARTOLDMONOO11070 o 1. Chemistry of PCB and their tocicology. 2. Analytical methods for rooiduo analyBifl and proof of structurco. J. Behaviour of PCB in nature, differenciee in metabolising rnto ......" of the PCB components, potenoation in an ecological oerie, con centration lovels and examples of samples which have boon proved to con tain PCB. A residue analysis can be divided ini ' ' 1. Extraction of the pesticides from the biological material, . followed by a careful cloaning-up to take away interferring substances, most often fats. *a 2. Identification analysis by moan of gaB chromatography. Thin- , layer chromatography and mass spectrometry. 3. Quantitative analysis. '. ' . At on ecological laboratory in fliksmuBfiet in Stockholm 1-2 g of a Bamplo is cut out of the biological material and transferred into a weighed and carofully cleaned test tube, and stored at -20 until analysis. Smaller O samplos have been used, min. 5 mg of body fat, and with dry materials Buch as hair, feathers, pine needles 100 mg are sufficient to reach the desired 10 ng/g level in residue analysis. In caBeB of water proofs 1 1. is used for reaching the 10 pg/g. level. B.1 (homog) In order to facilitate complete extraction of the fatty materials from tho biological sample, the doulbe amount of finely powdered anhydrous magnesium sulphate is added to the eampling tube, and the whole is'honogeniecd with an inBertable homogenizor. The resulting powder is transferred into a special Soxhlet extractor. After 4 hours of extraction the solvent is evaporatod, leaving the fat in a small weighed test tube at the bottom Sox. -tube) of the extractor. This fat is dissolved in methylene chloride in such a way that 100 ul (0,1 ml) contain 20 mg of fat. The 100 ul solution 1b now transferred to a little object glaBb, 3 i 7 cm, covered with a silioagel layer 1 mm thick, in order to fora a line 0,7 cm from one end of the slide. Inserting this thin-layer plate into a vessel the bottom of which 1b covered by a few mm of methylene chloride, the Bolvcnt will be sucked up in the dry layer of silicagol,_and at least reach the upper end of the plate. The fact is that the fat has a greater affinity to the powder on the plate than the chlorinated hydrocarbon have. -- and we get a separation. The fat being more poler than the chlorinated ihydrocarbons will never go longer than 2 cm before thfi TRAN 056038 HARTOLDMONOO11071 o 'si 2LDTI0H tubo 5 CO 6 go O o 0 aolvont roaclioe tho upper part of the class* Tho front of tho fnt appoaro quite vioiblo against a lamp, and with tho aid of a rcsor blado tho zone above tho fat ia tranoferred to tho olutloa tubo and tho chlorinated bioeidou absorbed on the powdor can non bo........ oluted by ono ml of othor. The concentration in sufficient for detection of tho chlorinatod hydrocarbons down to tho 10--12 g levol. Tho noxt atop in tho analytical procedure concerns tho ooporation of tho dlfforont chlorinatod hydrocarbons that tho Dcunplo may contain. Ao a rrnttor of fact, this is a broubloaome task. It is easy to eotimato what is not proaont, but more difficult to say exactly one. is proaent* V/e ouffor from tho nogativo demonstration, as Trill bo shown lator. , At first a few words about the separation of the components preoont in the sample and their visualization. _ Tho separation is accomplished by mean of a gas chromatograph fitted to a dotoctor that tranofero itB impulse to a recorder. Tho Bystom is shortly .described: A opirally formed glass tube pith an inner diameter of 2 mm and about 2 a in length is filled up by a support, covored pith an thin layer of an oil. The tube is heated in the chromatograph to about 200. Through tho tube a stream of nitrogen continously follons. When about 10 ul (l/lOO of 1 ml) of tho purified sample is injected into the tubo, tho components of the eample Pill be vaporized and go forward through the column with the gaB stream. As the constituents havo dit fferent affinity to tho column filling thoy will pass the column with different spood and it will take differont time for them to roach tho dotoctor at tho othor end of tho glass tube. If tho temperature and the nitrogon flow are held constant thiD timo, tho retontlon tin, haB a spocificwalue for a cortain compound. This is true, but unfortunatoly it is also a fact that two components can havo tho-eamo retontlon timo. This is one of tho bigger problems in gas chromatographic analysis of unknown samples, as will soon be obviouo. To make it possible to ostimato tho retention time it is noceso&ry to visualize the chlorinated hydrocarbons. For that purposo more or loss specific detoctors are used. ThB dotoctor eh. at ofton usod in postlcldo analysis is the so called eloctron capture detector, which can detect down to ono picogram (=> 10** g of lindan). Unfortunately this dotector ia not specific for chlorine, bu gives answer alco for oxygencontainlng compounds. The response here is muc lower but can be counterbalanced if the concen tration of the oxygen containing is much higher. TRAN 056039 Tho principlo for tho electron capture detector is shortly: At the end of the gas chromatographic tube ia placed a little tube con-- tninini? n foil tnnrin of tUnnium tritido. This in no-radiant. The o- HARTOLDMONOO11072 --TJ oo particles are reacting with the nitrogen molecules coming from the column. Then we get + Ng -- e + N^. Ovor the detector v/e have a tcnoion of 90 volt and by mean of the..electrons v/e will get a constant eloctrical current over the detector. This standing current is transferred to a ono-mV rocordor as a constant baseline. V/hon now a chlorinated hydrocarbon loaves tho oolumn this compound hao a high affinity to tho oleotrons and this moans that tho amount of electrons will diminish, and they v/111 diminish proportionally to the amount of chlorine. Tho electrical current will also diminish and this is noted as a peak on the reoordor. Tho area of tho peak will be proportional to the amount of substance in the sample. By moan of a standard injection it is now possible to compare the roten- tion time and the aroa of an unknown component with the retention time and area of the known standard. As eaid before this detoctor is not speci fic for chlrine but anyhow very useful, because of its high sonoitivity. Tho systom described has, as we have seen, two disadvantages: 1. Two different compounds can have the same retention time and bo dctocted as one peak. 2. A registrated peak does not need to be chlorinated , because the detector is not specific. If the sample is injected in two different columns with different chemical properties we have increased the chance for a good separation. If two compounds have the same retention time on one column they may not have it on another. When a result seems doubtful, - if the compound being responsible for a certain peak contains chlorine or not - it is possible to concontrate the sample and analyse /it on a less sensitive detector such as the microcloumetric one, which is specific for chlorine. The compound is burned in a furnace and teh generated chlorine titrated directly. As is seen from the two last mentioned possibilities it is anyhow possible to get a rather high degree of certainty in residue analysis, but it is t a rather time-consumeing work.When using this method just described, we very often found that many chromatograms from residue analysis of most carefully purified samples still contain a large number of peako. llany of these have retention times that do not agree with any knovm chlorinated pesticides, or their metabolites. This chromatogram con serve as an example. It was obtained by residue analysis of a sea-eagle found deed in the archipelago of Stockholm. In the range of the knovm peaks, there are so many unidentified that there also must be an obvious risk of the . known peako to be covered by unknown onen. Tf tM R remark 1 r. TrmnH +h Y-Arw-i*~+ rs-P nnn w .-nvin.m nno^i- HARTOLDMONOO11073 TRAN 056CH0 titabivo anal:, .As must be brought into queav in. In the precont investi gation it is shown that most of the unknown peak of chromatograms at residue analysis of chlorinated peoticideo oro due to polychlorinated biphonyls. I will ohow a cliromatogram of human fat analysed on a so called 5k 96............ ........................................................."................. .................................... ' '' ................ "` * column, the most ofton used typo in pesticide analyses. Early retention times wore in agreement with DEE, DDTop and DDTpp. Next slido shown the Bane sample analysed on a QE-1 column. Now the former 2 DDT peaks have divided into 4 peaks, and two of th*'m are siill in agreenont with DDTpp and op., tho two now wore unknown. Logically, those unknown components were at first thought to be netabolitos of the insecticides. Against that spoke that noigther treatment nor concentrated sulfuric acid in other. This treatment made it rather euro that tho compounds did not contain oxygen. In Sv/odon residues of organic mei cury have boen investigate;: rather intensively in the Swedish fauna. As those compounds give very high responses to the electron capture detec tor it was also investigated if the unknown peaks could have a mercuric origin. It was found that the water-ecological series had high residues of both mercury (v/eotermork, Johnelo) and the unknown ones, when the same indivi duals were analysed. Anyhow, the pheasant suffering most from mercury poisoning only contained low levels of electron capturing compounds and thece belonged ' ' to the normal insectisides. Therefore the unknown could hardly be mercu rials or metabolitos of `them. As the eagle sample giving the chromatogram shown in fig. 10. could be estimated to contain DDT and DDE up to 13 g/kg in extractable fat, the amount of unknown compounds clso were suggested to be in the same range, and tehn sufficiently high to do a run on the combined gas chromatograph mass spectrometer. If this could be done successfully it would be possible' to get very important informationsabout the chemical nature of the unknown, for ex. the molekular weight numbers of chlorine etc. This method is up to now the method giving the highest degree of certainty in the low level analytical chemistry, amounto of 100 ng substance being enough. TRAN 0 5 6 0 4 1 As thiG method for identification of totally unknown residues surely will be very important in the future (when f.cx. a biologist has found that fishes in a river die) it maybpossible by mean of this method to find out exactly what compounds are responsible for the death. For this reason, I will go into come details with this method. In the actual case we took the extract from 20 mg eagle and concentrated HARTOLDMONOO11074 ( Y* (.) o It as much as possible and made an injection on the gas chromatograph combined t/ith the mass spectrometer. The result was the chromatogram shown on the next slide. Every time tho recorder showed that a compound -............is loaving the column, the effluent is led to the tunes spectromotor. Now Just a fow words about tho mass spec. '* O D Tho molecules leaving the column are bomded with electrons at E. Wo have now got the molocule positive charged, but with the same maoo an before. This M+ is accelerated in a vacuum and will then get a kinetic enorgi. whero is the speed. Next comes the magnetic field that trios to bend the direction of the molecule. This v/ill be big for.a small molecule and less for If we have a siove in the other end we can directly read the molecular weight. Added to this parent molecule M+ we v/ill also got addition in formations, because of the fact that hl+ may not be stisble, a part of thorn will be broken down before they reach the sieve in the other end. F.ex. M,+ DDT M DDT - CC1. Mass spectrograms from the different unknown peaks in tho eagle sample as shown. Tho mass numbers equal to the molecular weights of the unknov/ns could be read to 426,392, 358, 324. Astonishingly, the molecular diffe rences were constantly 34 mass unitB. This difference shows a familarity in origin of the unknown. Now the fact is that chlorine exsisto as a ............ mixture of two isotopes with atom weights 35 and 37 in proportion 75s25. If the molecule haB one chlorine, this will give two molecule peaks, one for Cl,, and one for C1,_. If thore are two chlorine we have the possibility 37 _ of one with only ne with both Cl^ 81X1(1 ^7 "d one with 2 d^ and therefore TRAN 056042 HARTOLDMONOO11075 \jtr () o O 2ho relation of the poaks found on tho different mass epee woro: Molecular weight '' 324 358 392 426 Chlorino content 5 67 8 Ah erpldhation of the familiarity of the compounds can be given if one substanco is built from the former by substituting a hydrogen with chlorine RH 14+ * C12 + HC1 M + 34 Thon it is possibD io calculate tho molocular weight' of the parent . hydrocarbon PHC. Mpj,^ * M - x + x , where l& 1b the molecular weight of the conponont having x chlorine atoms. F.ex. for m = 426 and 8 Cl we will get " 426 - 280 + 8 o 154 and equal with the other molekylB. Tho moot probable formula with carbon and hydrogen giving this molecular woight is C12 H1q and `this can only be satisfied when the parent-hydro carbon is biphenyl, and the unknown being polychlorinated biphenyls. This explanation was later fully verified by injection of a eynthotic FBC on the mass spec. Furthermore extensive gas chromatographic investigations provod that the FBC standard gave peaks with the same retention time as the unknown poaks from the sea eagle. With the method just deocribed I suppose that wo have a new possibility to etudy the residues in the air because the pine needles can allwaye bo . We have had great difficult; in quantifying the FC3, but when getting a little more time it will be possible. We have done a few calculations on a few BpecieB, and 1 suppose they are right within a factor 2. We have found the residue to be from It hae been my statement here to-day to present this method for studies of defiling of the nature, and with this method a new typo of defiling agents has been found to be present in nature, and a few experiment have shown where they may bo found. Now this method is going to be used in the first hadn to estimate how the situation is in nature as a whole, and in the other hand to find the leaks throug which they find its way to naturo. Soen meybe are present here today to get news about the leaks, and to them I want to oay come back in a year. TRAN 056043 HARTOLDMONOO11076 (b 9. So much I think I'can cay again that the PCB hardly can cone from agriculture. As support lor this auggeotion I can say that we have found PCB in oaglo foathers from Riksrauceet from 1944, where hardly any .................. chlorinated pesticides were used in agricultrue. One moro thing that I find important to say is that in contrast to the mercury problem this dooo not ooom to bo a pure Swedish problem. I have Just studied chromatograms tokon from London air, and they dourly contain PCB, and dr. Holdon hun told mo that ho also find them in his fishsamples. But finally in waiting at more results Inshould like to pointHSe morething. It is proved that PC comoo to naturo, wo dont know now where they are usod, but thoy are vory persistant to chemicals and to fire. I think the poison Jury Bhould try to state that a content of PCB shall always bo found in an open declara tion. TRAN 056044 / HARTOLDMONOO11077 HARTOLDMONOO11078 z c> ) N) Cj 0 VtUJ c. i ^s ^ N k3 N t\ o\ * >. <o *b I' a Kt & i u b *bs c> "V rv <*> ^. cs II I 1II o ^) TRAN 056046 HARTOLDMONOO11079 TRAN 0560<*7 HARTOLDMONOO11080 o V V* <x v <* * Ov hi 'O U* v' % s * o K> U. *?->* Jnj VAjr\$ I s Ci Z Sajdq < vi > / sm jr> o <: > t' C) * o 1 3 . -> o *b i' N > A'/V O ltf > ______________ . ________________ ' > TRAN ) 056048 ' o HARTOLDMONOO11081 HARTOLDMONOO11082 c"> *N o -Cuzx-d CL i C-*JN <vN. 1 ^-Cr-u-r^e r o i \ N Cvr-r-c j. 6-u^xlc. <? ty- ^ N k Q> Q t k %k \ A: Q vl O K I > s #SJ C-> '`a K *s n k \3 ^ <N L /A/Dfl/JF TRAN 056050 HARTOLDMONOO11083 LffSD/W t O Q w ) i 0 1 U. O' TRAN 056051 HARTOLDMONOO11084 i I, ii i !j 11 ii O HARTOLDMONOO11085 o \ I i I HARTOLDMONOO11086 1 HARTOLDMONOO11087 HARTOLDMONOO11088 -f >-? )o 3- O' asV *\ S' IRAN 056056 HARTOLDMONOO11089 ) t -S' 5> ? \0 %^ 3 v>r.\' \ TRAN 056057 HARTOLDMONOO11090 o O 1-I 'S. -t L, V ^ .v* .Q & oo" o* o &' J-- *[ *5:i / / Jl * v>> TRAN 056058 s HARTOLDMONOO11091 ) a TRAN 056059 HARTOLDMONOO11092 rm *5 C (Z VO' ^_-L TRAN 050fe HARTOLDMONOO11093 - O j> (/ V/ O o t . . - * TRAN 056061 HARTOLDMONOO11094 CHtMfNTATOI 0 (D / PV ~ ~^A *> - / FTcT*- - - -- /'/3%7 ^++*3 I* io*Conservationists have another chemical to worry about, one that apparently accumulate* fa fish, birds, animals and people much like DDT. Called polychlorobiphcnyl (PCB) kac -In Sweden where its presence in nature ..was ..Brat discovered, the chemical is " known as chlorinated biphenyl in the U.S. Though not made in Sweden, the chemical Is used worldwide in transformer oils, lubricants, paints and solvents. A Swedish scientist says PCS first appears in museum-preserved sea eagles dating from 1944, and that It Is now present in high concentrations In fish, fish spawn, birds, seals, and human adults and children. The Swedes attribute wide spread distribution of PCB--it has been detected in the air of London and Ham burg, and in seals off Scotland--to air pollution resulting from industrial uses and from incineration, which does not destroy the chemical. The extent of the t /' / hazard, if any, is not known. And U.S. sources say they are not aware of any . such problem in this country. / "Taka m# to the moon" remains a wish In song only for most women, except for the J<r/rn or SO who joined about nine, hundred men in answering the National Aeronautics .- and Space Administration's (NASA) latest call for scientists-astronauta (Cfirmen- lalor. Sept. 28, 1900, p. 59). At the deadline, Jan. 3, only 939 doctorate engineers and scientists had filed applications out of an estimated 20,000 quajified persons in the country. Engineers comprised 27% of the applicants. The National Academy of Sciences (N'AS) will pre-screen the applicants for NASA, which will select twelve of the survivors before August 15. No estimate of the women applicants' chances of selection is available. Even the United Steelworkers asked the U.S. Supreme Court to overturn an injunction that forced striking members back to work at Union Carbide Corp.'s Kokomo, Ind., plant (Chemcntator, Jan. 16, p. 81), the company appealed last week to a W. Va. court to set aside an unemployment compensation award to its Alloy, W. Va., employees. The W. -Va. Dept, of Employment Security said on Jan. 6 that 1,060 Alloy employees were entitled to compensation for the nearly three months the plant was shut down between July 2 and Sept. 22, 1906. The National Labor Relations Board had branded that shutdown as an illegal lockout , . (Chcmeniaior, Nov. 7, 1B06, p. 97). When Carbide reopened the plant, the " employees struck. They are still striking. I /7/ #w HXHIBfT HodlL *'Mr Pawtr plants and tht stilt of Nvw Jersey prt most 1 the blecne !nx high ro'dm dfipnS&r levels in the New York-New Jersey metropolitan area--the power companies because they produce most of the pollutant, and New Jersey because it has no . > rules to cope with the problem. . These were among the conclusions of the lengthy N.Y.-N.J. Interstate Air , ' Pollution Abatement Conference held in New York this month (Chementator, Jan. 16, p. 82). The Conference, though recessed, technically remains in session until a permanent body is established. Among the recommendations were these: . `Federal representation, with a vote equal to the states, on the interstate body. The U.S. wants an entirely new agency, while the conferees prefer to ' ' expand the authority of the existing Interstate Sanitation Commission. . `Application of New York's ambient-air quality objectives to the entire area. . ' '. `Power plants not to bum fuel exceeding 1% sulfur after Oct. 1, 1909, unless the plants are equipped to deal adequately with SO* emissions. `No new generating plants to be permitted unless a 20-yr. supply of . ' , '- low-sulfur fuel can.be guaranteed. New sources of SOt emission to be limited to 500 ppm., and existing sources limited to 2,000 ppm. ; - TRAN 056034 n ternary >0,1U7--CMmlctl (nylftMftay S HARTOLDMONOO11095 St. Louis February 10, 1967 <?. R- Buchanan - GBUCH j. riler - BRUSSELS >.V.N. Hardy - LONDON Mr. D. Wood LONDON We have had a rather extensive nesting, which included the St. Louis individuals receiving copies of this memorandum, on Aroolor in the air and in various fish and other living res ervoirs . The decision was that more information had to be gained, and whether this would necessitate a trip from someone in the Medical Department to the various agencies working on this problem in Europe would depend upon how easily obtainable these gaps in our knowledge are by other means than personal com munication . We are very worried about what is liable to happen in the states when the various technical and lay news media pick up the subject. This is especially critical at this time because air pollution is getting a tremendous amount of publicity in the United States. We have been receiving quite a few communications from our customers, but the most critical on# is NCR, * are very much involved with their oezbonlose carbon paper. I have listed a number of points referring to information I would like to have. Some of these may be easy to answer others might take a little bit of investigation and some might not be feasible to answer at this time. However, please let me know your ideas on each one of the following itemsi 1. Can we get the original articles in the Swedish press, including Dagena Nyheter? 1 have a good fluent Dane - who translates Swedish very well and is a physician and investigator, so nothing will be lost in the trans lation. ............................. ............... G ck)rrtsfiC- 2. Who were the participants in the eomtest referred to in your memorandum to Mr. Buchanan of January 267 Qnder whose auspices was it held and Wbrortbere any reports issued? What were the eondlusiens of the conference and was any action decided upon? 8SBk: AITIAL TRAN 056619 r an HARTOLDMONOO11096 Mr. D. Wood -2- Februsry lo, 1967 3. what via tha medicsl institute in Sweden th fc vm ' going to do tha toxicological work referred to in _..............the mum nemoronduA to Mr. Buohanan? Who was going to pay for it and what was the scope of the inveafclgation? ..... 4. In LKB press release of Janu&ry 10, they stated that 12 OECD nations ware going to do work on this problem. Can anything be found out about tha extent of t: is work? Who is doing it, and at what institutes? 5. What is known about the work In England at the Monks Wood Experimental Station and the Laboratory of Chemists in London? How long has this gone on? Is it an ongoing study? What are the perimeters of the study? 6. Do we have the complete paper in Swedish of Jenssen and Widmark entitled "Pesticide Analysis--'Presence of Polychlorinated Biphenyls and Residual Analysis of Biological Samples"? This was referred t? in D.V.N. Hardy's letter of January 12, 1967. I would like to get this original paper with the bibliography in Swedish. 7. Can I have more information about the Carlin Institute of Toxicology which was referred to in Mr. Widmark's letter to Mr. Ford of December 29, 1966? What do they intend to do? Who is the contact, end is it located in Stockholm? By copy of this memorandum, I am asking Dr. Hardy to find out what the situation is in the two English contacts referred to in Item 5. The consensus in St. Louis is that while Monsanto would like to keep in the background in this problem, we don't see how we will be able t*-' in the United States. We feel our customers, especially NCR, may ask us for some sort of data concerning /the safety of these residues in humans. This obviously slight be opening the door to an extensive and quite expensive toxicological/phamacological investigation. Before starting this, we certainly want to find out what is gcing on and not duplicate any of tha work. X have tried to call you for the last two -days and Xwiil J' ,out of town next^week, but X would like to call you the weak of the 20th. Perhaps by then you might have some answers to some of tha questions. COMPANY CONFIDENTIAL * lUSK/ln x*u,, m. d. ' TRAN 056620 m HARTOLDMONOO11097 RISING & STRAND GP/SO AKTI EBOLA.G TcucroNi J4 01 iv tcicohami himmi tiiui I4t KITOiM* I 44 41 MNHtmo* IMM4 Stockholm VA February 17, 19<-v7 Mr. David Wood Monsanto Europe BRUSSELS 3 Belgium Dear David, re: AnOCLORS Reference is made to our telephone conversation ar.d I have tried to dig out the information you asked for. Before going into any detail, however, I would like to refer to your letter to Mr. Soren Jensen , dated February 8. Mr. Jensen would be interested in samples of as many Isomers as you can put at his disposal. The quantities of course are very small indeed and he would need only about 10 mg of each. In theory you could put the lot behind a stamp and mail it to Mr. SBren Jensen but in actual practice it is of course not as easy as that. Anyway, Mr. Jensen would be interestedin both the lowchlorinated and the high-chlorinated types since this would help him to get a better picture of the metabolism. Now to the various points you raised. Enclosed you will find the original articles as published in "Dager.s ____ Nyheter" and "Svensaa Dagblaaet1' on November 2?, 1. The people who organised the meeting wnere Mr. Jor.sen's paper was presented was a Committee - 19t-4 Ars NaturvArdskcmmittA - operating under Statens Naturveten3jcapii Forskningsrid (The Swedish Natural Science Researcn Council). The Committee (for Conservation of Natural Resources of 1964) is working under the chairmanship of a Dr. B. Lundholm. .............................. .................................................... The meeting was organised under the auspices of Naturvdrdskommittfen and was called apparently only in order to give Mr. Sbren Jensen an opportunity to publish his findings. The timing was made so as to coincide with a visit of Dr. A. Holden from Scotland. - Cl>oo4 EXHIBIT NO.Aill X COMPANY TRAN 056616 ..... 1 CONFIDENTIAL l . HARTOLDMONOO11098 ing a. strano Mr. D. Wood - MCL Dr. Alan Holrivri - address Fresh Water Fisheries Laboratory, "Pitlocnry Pearcher, Scotland - is the coordinator for the twelve OECD countries, as far as the Influence of biocides. on Nature goes. Dr. Holden apparently is a specialist on auch questions and particularly on fish. There is no Intention that Dr. Holden, or the group of twelve OECD countries as such, should carry on any further investigations on the particular problem unearthed by Mr. Jensen. Any continuation will be carried on in Stockholm by Mr. Jensen or cooperating Swedish labora tories. The meeting of November 2J offered only one paper, i.e. that of Mr. Jensen. No decisions were made on any further action. The work done by Mr. Jensen was paid for by the abovementioned Committee for Conservation of Natural Resources. The further studies planned for on toxicology have not been started on yet since there is no money available. It is possible, however, that the same Committee of 196^ will be asked to subsidise even that work. If toxicological studies are to be made, these probably will be carried out at Karolinska Institutet, Division of Toxicology under Professor Bo Holmstedt. The full address of this institute is Kgl. Karolinska Institutet Avd. Toxlkologi SolnavSgen 1 Stockholm 60. Since no decision has been made on toxicological invest igations, obviously no information can be given as to the scope of the planned investigations. The LKB press release of January 10, 1967 mentionec the research of twelve OECD countries. As was mentioned above, there is no question of any central investigations to be made under the auspices of the twelve countries. There is only the question of coordinated efforts by way of interchange of information. Enclosed you will find photo copies of the original paper of Mr. Sdren Jensen. We have taken this copy here and Mr. Jensen apologizes for the state of the paper which is his own typing. He has not yet had an oppor tunity to have it properly retyped for publication. I hope the above answers your questions. Yours sir.cvrely. CQMPamv HARTOLDMONOO11099 0 rising . strand Mr. D. Wood - MCL T. P.S. David:- ... ......... .. ... . ...-................... -......................................... - For the sake of good order, I would like to mention that Mr. Soren Jensen has sent us these papers with the understanding that they are only for internal use within the Monsanto organisation. Ola TRAN 056616 HARTOLDMONOO11100 St. Louis Fabruary 21, 1967 Mr. Gana Hilda CHILD G. R. Buchanan - CBUCH R. E. Xallar - QUEEN? X talkad to Dava Hood in Bruasals this morning and X list below tha saliant faaturas of our conversation! ' 1. Ha has 90% of tha information askad for in my lattar of Fabruary 10 and will hava the rest obtained in tha next day or so and will forward tha bundle to me. It should arrive within a weak. 2. His customers in Europe are seemingly lass concerned than they were, especially since there * has bean no particular government activity no increase in the newspaper articles. The customers would like some reassurance on the toxicity of Aroclor (I explained to Dave that there just was no information available on the action of nanograms of Aroclor in the human body over a lifetime). There is no toxicological work going on at present in Sweden and it appears there is some likelihood that it will not be able to obtain financing and might not be dona. Everybody over there is 100% convinced that what Janssen and Hldmark found was Aroclor. 3. There is no necessity at present for anyone from St. Louis to contact the Swedish people. In fact, it would be unwise at present. I am to get in touch with Kr. Hood after I receive the bundle of information ha is sending ms. unless somsthing unusual happens in the United States, I vould be of the opinion that we should do no further action until we have time to evaluate this information. REX/ln X. Ssnst Kelly, M. D. IRAK 069966 m HARTOLDMONOO11101 Pftcte eddrzst wy rtpiy (a THt OOY1KMMINT CHIMIIT quett: Your reftrfict; Ministry of Technology LABORATORY OF THE GOVERNMENT CHEMIST ... ....... - Cornwall Home, Stamford Street. London S.E.1 Telephone: WATer/oo 7900, ext. ftflf- RECD27 FED 1967 2Jrd Tsbruary, 1967. Bear Dr. Hardy, Tltb reference to your letter of 20th February to the Covarnmant Chastist and our dlaousslon on the telephone the following day, I eaa confirm that we ere very Interested In thle Laboratory In the suggestion by Jenaen of the Dniverslty of Stockholm that ohlorlnated biphenyl oospounds ooour in wildlife. As you are aware, we have for eoeM years been ezanlning aeleetad fooda, huaan tissue, wildlife, eto. for organoohlorine pesticide residues. The work on food end human tleaue has been oarrled out on a systematic basis for the Scientific Bub-oeaaittee on Poisonous Substanoea used In Agriculture and Food Storage, while the wildlife work la for the Nature Cooserraney. He bate found that wildlife, in partioular, often oontains a nuaber of ooepounda which produoe a ssriee of peaks on gas chromatograms when using eleotroa-eapture detector*-. These peaks do not correspond to peatioidea or their known breakdown products or metabolites but they souetiwes Interfere with the do'eruinatlon of the pesticides. Ve have spent ooe tiao attenptlng to identify th -.a unknown oempounde whioh ooour at quite low lewela, probably parta per nilllon nost. Their close eiailarity has presented us fron Isolating indiwldual conpounds but, collectively, we know they have a , high chlorine content - about 50f - similar to the organoohlorine pesticides. This led us to think that they wight be derivatives of suoh peatioidea aa DDT or dialdrln beoaute we nevar aeeaed to find then without one of these aleo being preeent in aubatantial amount*. V* alao oonaldarad that they night be oonpounda of the peatioidea with aterol or protein neterial or be polynere or inter-oondensation produots of the peBtioidea, W mSCaJr . Experimental work failed to oonflra any of theee hypothaeee end being short of staff we abandoned the work until we obtained a positive lead. Jenaen'a announcement caused us to examine e saaple of Aroelor Be sin whioh wa found in another eeotlon of the Laboratory. Vs find it gives peaks on the gai ohromatograph fairly oloaa to those which arc given by avian liver end we are now oarrylng out further work whioh look* proalelng but he^ whioh it would be foolish to prejudge. Sven if ve find Aroolor ooapounde to be responsible it will raise a nuaber of isporient questions such as how doss it get there and why aainly bird life, end sons Karine life like seals, end so seldom in nan or hi* fooda such as ailk, butter, eto, Ve shall be pleased to examine any further sample* of Aroolor which you cemd ua and 1st you know th* results. I enclose a reprint of the section of the 1965 Annual Hsport of this Laboratory whioh may be of Interest to you. TRAN 056615 Tours lmoerely. Dr. D.V.N. Hardy, Monsanto ChaaioalS Ltd., 10-18 Vlotorla Street, S.V. 1. J.O'C. Tat; HARTOLDMONOO11102 iO I ) \ ic ! I t1 > PESTICIDE ANALYSIS . PRESENCE OP FOIYCJLLOHINATED DIPJffiirYLS AT RESIDUE ANALYSIS OP DIOLOOICAL SAMPLES. ...........'...............................:.................................................................................................... Sbrcn Jenocn and Gunnar flidmork Inotituto of Analytical Chemiatry, Univorolty of Stockholm, Stockholm 50, Sweden. ` (Synopoiu) . At annlyoio of samples from the Swedish 7/ild-life fauna by means of gas chromatography, uning both alcctron capture dotoctor and micro coulomc- trie detector, a large nvunbor of unknown but chlorine containing compoun have boon dotocted togothor with tho ordinary pesticides. Uaospcctro of oomo of these compounds obtained at a combined gna chromatograph mass opoctromoter (lXB-9000) indicate that moot of the unknown compounds nxo polychlorinated biphonylo, potentiated somewhat in naturo towardo tboGe of hlhor degree of chlorination. . . A large number of samples have been examined, and polychlorinated biphen aro found oepocially in fioh and in sea birds but also in noodloo of con forD and in oomo samples of human depot fat. Two hundred samples of ooil and water did not contain detectable amounts of chlorinated biphenyls no did twenty samples of tcrrootrinl mammals. By tho uoo of a nitration mothod most of tho ordinary pooticidoo can bo romovod from oxtracto, loaving tho polychlorinatod biphenyl unaffected. Using this mothod, it has been shovra that two of tho major peaks of tho chlorinated biphonylo overlap the two pooka of ppDDT and opDDT rospectiv ly. This is found true for SP-96 columns, moot frequently used for tho quantitative rooiduo analyses roportod in litoraturej not in enno of QP-1 columns. . . ' TRAN 055798 y HARTOLDMONOO11103 TRAN 0 5 5 7 9 9 HARTOLDMONOO11104 f> JNSTJTUTJi OF ANALYTICAL: CHEMISTRY UN1VKHS1TY OK STOCKHOLM UolAgfcvSgeft 90t Stockholm SO, Sweden 6). Vl... Stockholm, February 27, 1967 Mr Gene C.'.Vilde Plasticizer Sales Dept,........ Monsanto Co 800 Lindbergh Bid St Louis, Missouri 63166, OSA Thank you for your letter of January 24, which was on my desk when I returned from a lecture trip to Germany, During this trip I gave a lecture at Bayer AG, Leverkusen, a company manufacturing polychlorinated biphenyls under the trade name of Clophcn A 50 and A 30, During the intense discussion v/hich followed my lecture there were no objections to our analytical findings except for the possibility of one of the PCB . . isomers to be formed at the decomposition of Lindane; over three chloro benseno. Although yie do not have a scientific proof against this assumptio made by an application chemist of Layer - I think the reaction is very unlikely and only responsible for one of the PCD isomers. - The chromntogr added to this letter demonstrates the increase of the higher chlorinated PCB's through a food chain and the decrease of the lov/cr ones; this is against the "lindane-theory". Remark also the non-prcsence of PCB in a non-nqunbic animal. At present we are discussing the plans for the toxilogical investigations to be done in collaboration v/ith prof. Bo flolinstedt, head of "the ; Toxilogical Dept, of the Carolin Institute. However, it is my firm impression that the toxilogical work to be done is of such a great extent that it has 'to be divided between more toxilogical laboratories. Moreover, .``more analytical work has to be done to aid the toxicologjca 1 work. During my visit to Germany your Swedish representant, Rising and Strand Co (Mr O.Palm) has been in contact', with Mr Soren Jenson of this institute. At their discussion Mr Palm was given a manuscript of a lecture which Mr Jensen recently gave for the board of the Swedish Committee of natural Resources, A copy of this lecture has been sent to Monsanto. It has to be TRAN 055792 HARTOLDMONOO11105 underlined that, according to tha^wgraemant hetwf>n^than< two gentlemen thie manuacript must only be i^^Tae--in8Tde Moneaffty Please inform your collegues..of Monsanto of thdys iiiil Sincerely YourB Cunnar Vidmark tm* s"3 HARTOLDMONOO11106 TRAN 0 5 5 7 9 * r HARTOLDMONOO11107 Bans Wild* - General Offloes March l, l$6f 0. H Buchanan ___ v **' V, H. Bunt S POLYCHLORINATED BIPHSTTLS --^R. 2. Seller - JPQ v. ?. Mayohe^?' twrwnism of Stockholm # 'X * r ' Or* R. i, shelly .............................' ' '................ Attached la the latest ooaaunlque that Z hare received tram Guonar uldaark* Z thought you would be Interested In receiving a copy of this about Wldnark*a visit at Bayer* Aa you can see he says that there wi quite an Intense discussion, which Z can Imagine- about the recent publicity from the university or Stocttvola and that there waa oily one objection which involved the possibility of one of the polychlorinated biphenyl, laoaers to be formed at the deccseositlon of Lindane* Z suppose the nest Important thing in this letter is the second paragraph* Here he outlines future investigations at the Carolln Xhsti* tute and he believes th#re will have to be news laboratories brought Into the project to complete the Mix* If any of you have any consent* or thoughts en acnething which should be done now, please let ne know lnaedlately, X have heard nothing wore from our evetoners or fran the field since our nesting la your office* The only U* 8* publication that carried the stoiy be date has been "Chemical Engineering", thank you for your cooperation in helping us fellow this so that wa oan protect our interests properly* Gene rv TRAN 085999 HARTOLDMONOO11108 W 7~~> .. --.fc."--H-.liwir,m.n. m. * * * K ii:pac fOMMiRKifix on* Minimus 01 i-ksticidk ui-smiiK anai.ykip ... ....... PESTICIDE RESIDUES 10G7 IUPAC CommiKKioii on the Development, Improvement', and Slnntlnrtli/.nlioit of Melhotls of Pesticide Residue Analysis Jly 11. KG AN, ,Secretnr)/ 1o ihe Commission (DnliornUiry of the Government Chemist, Comwnll 11 Sl/iinford Sl.t Iximlon, S.E.l, England) The first. iniTlingii of the above Commis sion of the IVsticidc.s Sect-ion of the Applied (')ieniislry Division of HJJ'AC were held in Grnevn in November JflGG under (lie chair manship of Dr. II. A. K. G.'illey. The follow. iiiC nrcount. of fhr proceedings is Imsed on the mimilrn of the nieetnip nnd on the ap pendixes presented l>y the. members nnd associate members of the Commission ns imlicnled. . 1. Foiiiignnl Hridflur AnnlyntM The ColiiniiKsioo Agreed I hat it was doe.irnhlc to develop rapid, sensitive mnltidetec (ion systems of no.slysis for residues of j fuinignnls aiteli as methyl bromide, ethylene dihromiilr, ethylene diclilnride, ethylene oxide, Acrylonitrile, carbon Ictrnrhloride, ratboo disulfide, mid phosphine. A study of Iho (ip]i)iention of gas-liquid chrninntograpliio met hods was thought to Is-, worth while. A need for simple nnd relinlile "on ; site." test equipment, was also discussed and ntteiiliou was drawn to limitations in the n.uo of roiimiereiHl iiidir.nior tubes for measurement of residues in (.rented produce. 2. Diphenyl Itcsulur Analysis l. The Commission disrtixsed progress in Lite ' study of methods of sampling nnd analysis of citrus fruit, for residues of diphenyl. A preliminary report of'the Netherlands Cen tral Institute for Nutrition mjd Pood ](c search T.N.O. indicated thnt, of tlie two inrlliods studied, the gas chromatographic method was the faster nnd more nr.rurate; however, the thin layer chromatographic method followed by ultraviolet spccirn, jihtiluineiry wiis also suitable. Work on , sampling boxed fruit had been completed and investigation of sampling procedures for shiploads and other consignments was in progress. Holli met hods of residue analysis appeared to the Commission to be acceptnblc. 3. Orgfinomcreury Fungicide Itraidur. Anaiyaia KcguIaUiry methods for orgntioincrcury residue analysis were discussed; it was in dicated thnt while radioaclivation facilities for this were adequate in Scandinavia, gasliquid chromatography offered considerable promise both for high senmtivity and high specificity. The neutron aclivnlion methods were probably the liest where facilities were nvnilnblc but, like the nctvor cold vapor atomic absorption techniques which were likely to bo cheaper and just as sensitive, did not. distinguish the form in which the mercury was bound. Jn the United States, the Pood and Drug Administration mndc a direct comparison between cold vapor atomic absorption and neutron activation tech niques; the Association of Official Analytical Chemists had recently appointed n new referee for mercury residue analysis. t. Orgnnochlurine Pesticide llctiduc. Analysis fa) Krainatiun--fry /. William Cook (Dirttinn of Food Chemistry, Food and Drug Administration, Washington, V.C. 20204)......... . Much progress has been made in Uie de velopment and refinement of methods of analysis by which any or all of a large num ber of jrcstieide residue chemicals can be detected and measured in one genera) opera tion. lltcy have come to bo known *5. "nmliidetcctiwi" methods of analysis. The following discussion includes DDT, y-HHC, aldiin, dicldriu, hcplaclilor, endrin, clilordane, cndosulfan, and mntiy other chemicals. There arc a few hundred pesticide chemicals in use; some of these consist of more than * - t* :r k P/f~ fcoed EXHIBIT HO ^ iff 1 X/'/o/trA TRAN 056026 r Tn fr. HARTOLDMONOO11109 r & i : h ELL_i / s 1/ . Ji 'j j ' 1 : .r-f. 4 'i* .i . ' -y | _ ' : > ... ' ' 3 JOOK .lOl.KKAI. OS Till. ( Yol. Xo. ,\ I otic compound and some convert to a senes of alteration products whirli may appear m residue analysis. Therefore, there is a large imtnlter of ehcttticnl6 which chii show iij) ill a ninllidrleelioii me.Uiod of analysis Whether or mil they me sigitifirHitl ns residues, 1 heir presence must Ik: recognized in order lint to confuse them with significant jieslieide chemi cals. Ideally, a general method of analysis whirl) would measure and identify all of the signified ill. residues in all food products with a minimum of analytical effort and time would he desirnhlu. 'Jliis is not possible at the present lime, but some important achievement* in that direction hove been obtained to date. The developments no far havo made it possible to rxtrart, clean up, inensure quan titatively, and give a high dogrc.o of certainty to the identity of the compounds for op to 100 pestirule residue chemicals obtained front a great variety of food crops and product* all in one genern) operation. This has been dime with either extracts from individual prndurts nr rotuposilcs nf a large, nundter of produelK, c.g., "total diet" or "market basket" samples. The development of kuc.Ii procedures lias required a tremendous amount of ciTorl. At each point along (he way choices find to be. made. As ft c.onse- t|iience of these elioiers, adjustments in the lotnl proeeilure have also had to he made. The choices may not necessarily have, been the be*! ones, ltul ns the total procedure developed, (lie more diflicult it Uranic tu undertake any substitutions. Many of the steps add to the certainty of the identity of the chemicals os well ns to the quantitative measurement. The extraction and flic clean up procedures roust yield quantitative recov eries of tlie chemicals. The gas chromato graphic systems--that is, coinhina lions of column packing, liquid phase, temperature of operation, kind of detector, and oitcriiiing parameters--are. all highly important when one is attempting to obtain quantitative response from a number of chemicals. Condi tions whirli may he satisfactory for quanti tative results on an individual rlirniienl or a small mindirr of chemicals nmv not yield adequate quantitation for all of many clirmicals. . The. eollahorative study of miillidctc methods is not. as straightforward a* "wet" methods, of ..analysis. 'Hie nisi. snn]ile procedure that has hern nseo AOAC and oilier groii|ts fur de.-igu eMT.uiion of eollahoialive slmlies is gem not applicable to these utiilliiielertioo ccihires. It has been the eX|H-rienee of 1 and some other groups that if the dt of the procedure are not described e.\s and if they are not. followed closelv, g variations in the analytical results are t,Third. At the last AOAC meeting, a spe conference was held to discuss the jimli involved in rollalmi.'itive slmlies on il methods. It was devilled thal a special reft for collaborative studies wmild lie appnmi lie would work wilh Hie specialist in mi'll< itlogv- for tlie orgatiorlilonncs, oiganopl jthnlcx, herhirides, rlr,, to route tip with 0 procedures which are ready for rollahorai study if possible, and flien dese.rilio tl. prneedures, obtain collaborators, snl>. sninplrs, receivo and tnhulate data, etc. was proposed and accepted that if mrmb of lUl'AC were available to pnrtieip.-ile tliis collaborative elTort they would hr w coined by AOAC. It. is anliripnlcd 11 I i program will heeoine elleelive early in J!i ll. will prohnhlv inrlude ext rael ion, rlratn lltiu layer rlirnniatoprajibv, and gas do inalography. (Ins chrnmalogrnphy will involve the o of an electron capture del erf or nnd n lh> mionic detector on a split, stream or in t:> desn so Hint n. separate but sinnihniiro readout for both organoe.hloriucs anil organ phosphates will be made. The aimiiltanein readout from the two detectors adds to t! certainty of the identity of the compound Tor instance, parathion gives a large isjuiiikc on the. thiTininnir. detector due to H phosphorus Binl ft much. Rinnller response < the ICC detecUir doe to tlie NO; group, 'll presence and ratio of these two jtenks aliu. with retention time are quite chararten.-ii. Likewise, trilliion gives resjionse by but detectors because of the jthnspliorus and th chlorine in tlie molecule. Again the rct-eniio lime and ratio of the two responses enli.im identiliralion of the coinjiounds Inin Analyzed. f.' . a TV sly-! '-"v . TRAN 056027 ^ I'' .* "rvr'"*-- ir i rwtiiM Hi HARTOLDMONOO11110 __ ^iV.; Aw m/tm'm miwttmWuJA <Us stlrtf^s. Il'I'At* COMMISSION ox MKTJlilMK OF IT`.S*TK*J1>K JlKKIIlUr. ANALYSIS MHH) (It) J'omiblr Intrrfrrrnrr by Cbtonnhfrrf Wftbrrirh--by 0. Widntatk (inttitutr. of 4oo(yticnl (IhrmiKtrr, Vnlt'ertity of Stirbhffirn% 0(tf Stockholm no, .Sirftlrn ) A large imnilier of unknown but chlorinccniitniuitig rniupoumlR have Imi detected in addition In I lie ordinary pestiridrs in the analysis of samples, using liotli (lie electron rapture. and tin* niirrnrnolnmrtrir (Irl-rclnr. Alass vj H'fl in nf **mir nf those. cemj mumIn nblniiied mill ;i nmil'inrd gas chromato graph-mass )(< Icr (ld(li-00(XI) indi ruled tlml. most of llie unknown compounds nm polyrhloriimted biphenyls, potentiated somewhat in mi I n re towards those of higher deem: nf rhhiriiiation. A large nnnilier of samples have liven examined. I'olyrlilnriiiated biphenyls are foimd eeitrciiilly in fish nnd in sen birds. lull- also in conifer needles and in sumo samples of lnnn:iii depot fat. Two hun dred Mintfi(cs (if soil and wilier nnd (wellIv samples of terrestrial mammals contained uu deleytnlile iiiiioiiiiIk of rliloriiialed biphenyls. Typical (! t A". Imres nrc given liv Jensen and Widninik (1). Ity using it nilralinn nietliod, mosl. of the ordinary iieslieides ran Lie ve- inoved from extracts and the |iolyrliloriiiii(ed biphenyl will In' iiniilTerted. hi tliis wy, il has btvn slnnvn tlml two of tin: major chlorinated biphenyl peaks overlap the peaks of ji,ji'-1)I>T and o,;/-])))T, rrs|vetively. This overlap is found with PF-Dfi rolmnns, must, frequently used for the quan titative residue analyses rrporled in lilorsi(ure, hut. not with QF-1 coliimns. (r) Confirmation */ Itfrnlily-- . by k. K. ClItnr (Shell itrtrnrch Ltd., ff'otnlttorh Agriculture Itrimrek Centra, Sillinubournr, Kent, England) Midtidelection methods would mein to lie essential for the analysis of orgimorlilnrinc residues lieeanse of tin: milnlier of clilorinnled r.oin|ioiienls which can U: present in any one wimple. However, lliere are problems of interpretation even when techniques are used with the resolution and sensitivity of electron capture GIA5. lor exaniple, the. . resolution of tin: 15)At column may not he sharp enough to separate eoiiijHuienls; or impurities piesent in (he tcrlinieul peslieide or other natural prodncls present, in the ex tract, may complicate the, analysis; or some inserlicides may thermally or catnlylically decompose during the analysis. For these reasons, residues of org.iriocliloriin: compounds should be confirmed by other analytical methods. If enough material can be isolated, infrared spectroscopy or mass s|>eetrosc(i]iy can give powerful evidence of identity. However, with other methods in common use Die physical basis underlying separation is very similar. lUihinson et al. (2) reported a highly significant conenrdanre between the "p-vnlucs'' for pesti cides in the various partition systems described by Hcroza and Itowriisn (3). Similarly, retention times on different GLC Hiatiomiry phases and 7t/ of pesticides ill various T1XJ or paper chromatographic systems are highly correlated. Further more, ff/ values in paper cliromalography arc closely correlated with Rj vulues in TLC mid with p-vnlucs. It is possible to do a great deal of work with the in tention of establishing the identity of a compound, but very little additional evidence will be gained because the results from the methods lined were not independent. G1>C retention time, an R{ value from TIjC or paper chromatography (or a p-vnlucl.a GJXJ retention time of a derivative formed by chemical reaction, mid pcslicidal activity against a susceptible organism arc considered to be independent parameters giving signifi cant evidence of identity. 5. Orgnnophoxphoru* Insecticide Itesiiinr - Analysis Tlie Commission concluded that while the. regulatory methods were adequate for pnrgUiion ami malntliion, clarification of tin: terminal residue situation would be welcome in some instances. However, more work on the dealn!]i stage for malntliion residues in eggs, milk, and dried fruit was indicated. 6- Dirlilorvos Kc-sidnc Analysis lly H. A Km Colley (Shell llrtcarch Ltd.. U Wilurk Agricultural llrrrnrch Centre, Sittinghourne, Kent, England) Five different approaches have been de veloped for the determination of traces of dichkirvos: tutu! phosphorus (4, 5), coloriin- TT miWi MMMhMI *:i in in'iitlimridigi 1.; I \' f TRAN 056028 HARTOLDMONOO11111 Y . \ Ir- M i H '"--a * 4 -i -I 1070 ctry using diiiilrophcnylliydraxuic. (G), RikaJitio -resorcinol (7, 8), sjiccjfic hibnssny (9). chnliiiPRlcr/iRR inhibition (10-J2), and gasliquid chromatography uitli the thermionic detector (13) Riid the lnicroeouloinelnr detector (14). Oil the basis of sensitivity, selectivity, speed, nnd possibility of multidrlccliiin, the most. suitable technique is Cl.C. Its sensi tivity (in the nanogrnm range with the. more sensitive detectors) is nppronched only by the e.bolincsternse inhibition procedure, mid it is unmatched on the other counts. How ever, there are two nsjiec.ts in the analysis of traces of dielilorvos bv G1X5 in which improvements are needed. These are the sup pression of decomposition of dielilorvos on the GI>C column, nnd the select ion of the best detector from'(a) cirriron eaptnrr, (i) tlicrinionic, (c) niicroeonlometrie, and (d) Haute photometric. The oilier sensitive method which is in widespread use (atul which, topether witti GIjC, offers additional evidence of identity) is the clinlinastera.se inhibition procedure. This is a general method for anticholinester ases; to analyze mixtures of inhibitors, separation before the analysis is required. However, the volatility of dielilorvos is such that if can be steam distilled front ex tracts even when they contain a high pro portion of fatty material. It is possible, there fore, to obtain a degree of specificity in the Analysis for dichlorvos by cholinesterase in hibition by incorporating a steam distillation step before the determination. _ Procedures for the collection' of dichlorvos vajior from the air, extraction of residues from crops and tissues, and cleanup are avnilnblc. Dielilorvos Jnay be quantitatively removed from air by bubbling through dis tilled water. Chloroform, methylene chloride, and benzene have been used to extract di- chlorvoa residues. Partitioning from an organic solvent into water, column chroma tography on silica go), nnd steam distillation provide adequate cleanup from fatty and nonfnUy materials. 7. ripmnj) Huloxidc ltniilur AnulpiN 'Jin* Commission recognized the mail for teli.'ilile methods for residues of pijxmunyl JOfKNAI. (JKTI!KA.().*.f. (\'ol.:>0 Kd .7 I ' buloxitle and certain allied nuiiriiaU'Vu. Allethrin nml MGK 245. 0. Ituilimi< livlin Mrilxnl- of Aiml,., The. Commission was informed tli.it liitoriuitioiinl Atomic Knergy Agency I l.\l had indicated tliat it would be prepaid (0) provide farililics for co-ordinating Inborative studies of existing ladionrtivm methods, (f) assisl organizations in the of Oetivalion techniques for the evaloai of analytical methods in general, and help laboratories wishing to rstablish i.-o. chemical techniques (15). It. was ngiecd ti while raiiioehemiral metfiods of :i n.i K were useful for mercury and fur brmn. residue detenninalions, they were vriv . pensive and not. necessarily more miwiivr more R)icciftc than some other un-tln* Moreover, although they were often mn in metabolic or field residue trial studs rndiorliriniral methods were in genernl i appropriate to regulatory methods of aiml sis; the development of various other met l>. of regulatory residue analysis was far m>. suitable. Jlen.uh'KeKK . (1) Jensen nnd Widninrk, Acta ('him. Sioml in press. (2) ItobillHOn, J,, Itiehiintsrm, A., and Khee K. 15., "Clii'inieid Identity in IdinmneiM Analysis," presented at the l.Vind Mei inu of the Anicricnn Clieinirni Knrnlv, Sep tember JDGO, at New Vork Cilv. (3) llownmn, M. ft., nml )Ionian, M.. 7Ai.Journal 48, 013 !)32 (100.1). (4) Jaws, E. Q,, nod Wfhley, 1). J., Annin>< 86.21(1-255 (lltfd). (5) Sftlmmn, P. M.. Anal tllirvi. 36, J l.'t III (IBM). ..... ^ (ft) lliigheN, J. T., A ualt/yl 88, HIK :ilfl (t'.Hltt I (7) Geiger, M,, slid Purer, It., 7, Atml Chr.m. 174.401-4(17 (t'JCO). (8) Itiie.hler, \\\, Jbir.lir, tV,, nml I'ijni, It, ibid. 213, 28-30 (1BC5). (9) Sun, y.-1*., ami Johnson, 15. It., Tins Journal 46. 524.530 (10C3). (10) Gimig, P. A., nnd Unit. S. A . Amil. ft-,,,. 23,1830-1834 (1951). (11) Citing, P. A., Smith, K uod Hall. S. A . J. Apr. Food Chrm. 4, 02I-C22 (Mi5i;i (J2) l'orlcr, 1'. 15., "Vajtoim ln.-een, ,,l. IRAN 056029 J.,,*' >*, &, f ' r \ ` ' ' "* ,,k* ' ` ,e.' * ;;* ` . ' ' , mmmmuiarnk if Y Ml i jin* si iliWiaitoafitttil4MaiiiiW,-3l^lli' ii8TiiT1->^^'Mita*tAB^ HARTOLDMONOO11112 jMm* un'*c: commission on mktiioiis on rnsnettiK ursiook akai.ysis 1071 ___ UJV1')'\ ill Analytical-Mr.thfld* jnr J'cntiridc*, I'larit Growth Ilcgutatars, nin/ Food Ailtlitiiwt, Vol. 11, G. Zvvcir (K.d,), Ariidciutc I'rcjw, New York( JtlM, pp. 6G1-571I. (13) El-ltefni, A. It., mill Giuffrida, Diura, Thu Journal <8, 374-370 (10T.5). (14) Itoonc, G. H., ibid. 48, 748-752 (19G5). (15) "KiidiniwiLopcs in tlio Detection of JVsl i cicle Uesiducs", procvcdiiiR# of the I'mirl on tlic Usee of HudioiaolopcB in the Delrr.tion of Pesticide UosiHuns, Inter national Atomic Energy Archry, Vienna. April 12-15,1DGG. Illl'AC CnmmiKMon on Terminal Residues Hy II. MOAN, Secretary In flic Commission (laboratory of the Government Chemist, Com wiill House, Stamford St., Ixmdon, S.Ii.l, England) Tint first meetings of tlic above Commis sion of l.lie 1'iwlir.idrs Section of the Applied Chemistry Division of Illl'AC were held in (icnevii in Niiveinlter lOfifl under (lie chair manship of Dr. II. Ilurtig. The following ticeonnt. of (ho proceedings is based on the iiiimites of the meeting and on the ap pendixes drawn up by memlicrB find Associate members of the Commission ns indicated. 1 ' 1. Termini*] Cnrbnrnnle Itnddttc Tito connniKsinn discussed tlic present position regarding knowledge of the nature of the tcrmimil residues of cnrlinuiatcs, iu- flndiug carbaryl, ns imlicntcd in the evalua tions lielmv, and set np a working group to further this knowledge with particular re gard to the uses of carbamates in food production. '. (a) UralItalian--Jrr /. ITilliom Cook (HivUlon of Foot! Chrmittry, Food and ' l>ru( Ailminiiiralion, b ailitnfloh, P.C. 202011 ~ ' ' lu the earlier studies on enrharyl residues, both enrharyl and its hydrolytic product, l-naphtlinl, were rniiKidrrcd. Kesiriue studies on many crops showed that the quantity of I-nnplilhnl was small and difficult to sep arate fmin carbnryl. Tims, it was considered llint 1-nnplitho] need not lie measured separately fiom rarbaryl, 'I'oleranees for carbaryl established in the United Stales arc based on the assumption that the major part of the rrsidne is the intact carbamate. Since the establishment of the inilinl toler ances for carbnryl, work Iin6 been done which may have some, bearing on the quanti tative and qualitative aspects of tlm residue. bight, including artificial light and sun light, changes carbnryl. In the formulated state it slowly degrades under the influence of ultraviolet and sunlight to give several unidentified products (1). Crosliy ct aL (2) reported that ctlianol or hexane solutions of some incthyleArbamate inae.etie.idcs, includ ing carbnryl, gave n variety of cholineslerase- inhibiting derivatives when exposed In either artificial light or sunlight. The products were separated but not identified. Abdvl-Waheb and eoworkers rcjxirtrd that the nature of the surface, the light, and the compound nflcctcd the rate of conversion of carbaryl and other carbamates in vitro in tlic solid State. ....... . ... . / ' Since neither the qualitative nor quantita tive aspects of pliolodecomposition of carba mates have born established, Ihc significanre of these, studies in relation to current and future tolerances for carbaryl must await further study. Whitehurst, et al. (4), using the colori metric method of analysis sensitive to car- baryl, 1-iiaphthol, and J-nnphthol conjugates, concluded that when cows were fed a diet containing carbaryl, no residues, to the limit of the method, were found in milk. This was Pt `;A r f w i. i. S-*: f" *-' T-T 11 my l1^*.*?.'*'.w.nt^i. jjt.g[|gjpiyitwyiyi.tijiiin r fyy' nk'uii. HARTOLDMONOO11113 ,'itl. .Vi, Nii. ' f limllulit.,. gill forward ;,* I'i.K. 'Ilu* |li:iK' Imi-Ii l|.|/| l is fur di--tcu #*I*|i|m'i| j. |l, , , [llllltl iilrliTi jt,!! j.j _ experience (,f l i, x llcil if llir i|. i . , I iIi-M TiIm iI |*\ ,, nvcd I'liiM-ly, J.,, r;il riv-uJi, a(,. ,. meeting, ii -p. Iar*f*ll>s llu- |in,| ' . Mltdll'K (ill 11,, , ini. n k|hti:i| n 1.1,. iililil In- ; 11|u.11,1. , in ii,, i|... il ilirK, inu.iiii,].| . . nine 1111 ill, i, ly fur i- 11 Ii I... r , M il lIl'M'riln- 11......" almmliii.-, Mil.,, . II In 11- ill In, ii, | -d that if tit* Hit- * : |- lu (cm tirij jit. I*y WimiM |m> vi. ili(`i|i;aIrtl Ili.M W : live *;irly IH r* . *f nictom, c)i %i t .V, (hd c.r dl invnlw 11> . It'Hnr iMid : il. hlri`;nti r * l(ll Kttt1 (.< . [ltrini'* ;m<| i*na . Tilt* Mllillll.al" irlufM ni|U Ih " of (lir civ(*K n I:mc' lHt*i*h*r dm* ** litinllrr rrs|N.n . pi* NO., crniii* I' l\vt |w:*k*- d f [iivtc* rlirii:i*`t* * - . rrn|Hihsi* l> I* " fltn^plinriK .Md [icnin ll* n*l *** n*H|*uliM*>. cid* kniijmmiiU I* l( o0 ,v n*MMMiiii\ iv mi-'.'niimik i ir I'tyiiriMK m-Kiiit i: .wai.vkik MKHI ai/ifr /,iterfere.trr iii* Chlttrittaietf orTifhf.^natural products prciurnt in llic cx- i.yAsnd*--f.y f*. If itlntnrk (Intiilulr n/ l.'firiul*lrjr, Unlrrriilg ,,/ Itnalngtengen 'Jll. Stiieklmlin Ml. wifi.f . --^ Iraet nvjy comjiliealc the analysis; or rnmc inseefiridcs may (liernmlly or cataljl/rally '(leriiiuiiuse ilurinp I lie analysis. For these reasons, residues of iirpano- Lirrn'_uumlicr-of-unknown bill rliloiim*- rhloiiue roiiipoiinds should lie rnnfiruicil by naming rnmpiimid* li:ivr lirrn detrrtrd in ;!iikhi In Mil1 ordinary |M*lit*idrK in the ili-is of samples, using linlli the clrrlrun ,;iiirr .uni tin* luirriiriiiiliiiiirtrir. ilrlrrlnr. !.|m'i'Ir;i nf Huinr nf these rmnpiHiiids other analylieal mrllmds. If r'ltoopli malerial r--in lie isolated, infrared specl.rosrnpy or mass K|iertriisciipy ran pivc powerful evidence of identity. However, with oilier tnelhuils in mnininu use die. physical basis underlying ,'iiihiI with :i t-iniil linn I c.is -rlu'iiuialii- fri>:ir.ilimi is very similar. Jloliiusou ct at. ;..;.|i-iii:isk spectrometer (I,K 11-000(1) iiuli- (7) ri'imrleil a liiphlv sipnifiranl rou- .-I lli.'il most nf I lie iiiikiiiiivn cnmpimmls rnrilnnee liclwecn the "p-vnhirs" for |iesli- v |m|vi lilnriii:ili,il Iii| ilirn vis. jHitrnli:ilii| ritles in die various pari il inn" systems 1.1'S'h.il in undue limiiriU tlmne iif higher .;ru- nf rliliiriii.'iliini. A large ihiiiiIht nf i.n|Jrs have Ikk'ii I-N.-Iiiiini il. I*<ilyi'liIIniii.i 1 i-it tirrnls an1 fiiiiml i'K|H'i'i;illy in fii-li Mini in drserils'd by llernsa and Ilmvtuau (il). Similarly, refenliun fimes on different GLC slaliunary phases and Iff of pesticides in variuns TI.C nr pnj>er ilirumaloprapliii* . i lairds, Iml :iIsn in rnnifrr needles and in systems arc highly correlated. Further . as* samples nf human depot fat. Two Iniii- more, If/ values in paper chromatography *..| r;iiii|>t<-ri nf Hiiif .mil walrr nml twenty arc closely correlated with fit values in ,ii|i|i-k uf terrestrial mammals contained ini T1AZ and with p-valucs. It is possible *,rinhlr mninnilK of chlorinated liifilieiivls. r-.|Kr:il GWJsdurcs arc given liy .Tcnsrn anil V.fmnrl/f I f.tfy using a nitration method, .-I id N+ie'urdinary pesticides mu l>r tv >i*i*l from r\lr:iclK anil Ilia |>iilyi-|iIntiii.-iti-il ;.|*nvl will In' uiiiiffcrled. In tliiK wav, il to do a great deal of work with the in tention of establishing the identity of a compound, but very little additional evidence will be gained because the results from die methods used were not independent. GI.C relent ion time, an Rt value from TI.C or I<rn fIiowii dial l\vo of the major pajicr chromatography (or a p-value), a 1 l".riua toil liiplioiiyl |>ralri; overlap tho GLC retention time of a derivative formed it* nf /i.ji'-DPT anil o,;.'-DI)T, rorpor- by chemical reaction, ami pcslicidal activity .n*ly. Iliis overlap is found with SF-OG ' against a susceptible organism arc considered liiiiiini, must, frequently used for die qnnn- Lo be independent parameters giving signifi .'.iiivii reriiliie analyses reported in litrm- *Iml nut with QF-I ciiIiiiuiis. cant evidence of identity. S. Organopbospliorus In-rctli'illc Ilruuhir it) f.'iiii/frinnriim i/ Itlrntilf--l. ti. ti. Hffinr (Shell Itt'trnrrh l.ltl I t*dwitrlt itpr/rnllnrr Krarnrcfi (irnlrr, 'uincliimrnr, Kent. Knulantl) Mallidelcction inefliocls would seem lo be -.nlinl for die nnnlysis of orpanorhlnrine `"dura lieeanm of llio nuinlior of rhlnrinnted m|*menlH wliieh call lie prian-nl in nnv one Analysis The Commission ronelnrled that while the regulatory methods were adequate for psrnthion and malalhion, clarification of the terminal resitlue situs I ion would he welcome in some instanres. However, more work on the cleanup stage for malalhion residues in eggs, milk, and dried Truit was indicated. Min|Jr. llmveyer, tbero arc problems of *' `. 6. .DIcMorvos Itcsldiie Annlysis , -.irrprelatinn even when leehniqnes are Ily It. A. E. Cnllejr (Shell Reteareh l.ltl.. -id with (he resolution nml sensitivity of V'ootfttttek Apilrulturnl ttetenreh Centre. ''-rtnui rapture GT/C. For example, tlio Siltlngbourne, Kent, England) . 'KJnlion of the GI.C column may not be Five different approaches havo been tlo- ,, --'ip rnouph to wpiirnte eoniponenls; or votoped for tlio (Iclcnninnlion of traces of j nipurilies proieiit in tbc teelmieal |Ma>lieidc dicblorvos: total phosphorus (4, 5), colorim- I TRAN 056031 HARTOLDMONOO11114 t o 1070 joniNAi. ok mi: A.0.A.1;. (Vol. Jil), No. 5, jo,;;, II IVVI* ( I1M.MISM1 ctry U.-iiin 'linitn.pl,nnllivilr.izini! ((I), nlkn- buloxidc and certain all ini materials surh ,, (l)l)VI')", linr resiirciiml (7, $), f|crilic hioassny (0), nlletlirin and MGK 24.r,. . rrxtirulr., /' t clmlimvl erase inliiliilimi (10-12), anil gns- Finn! All'llll liil'iiil cJimmnlngrnphy with I lie llicniiiiinic detector (I.'l) and ||ip inicrucniihmictric 8. Hitilloiirtiviition AlrltioiU of Ann|^|% % j Acadi-inic I 501-179. detector (14). .....P" ,l't> The Commission was informed dial i|,, of Kcnsilivily, selectivity, International Atomic Enemy Agency (J.(|;\,...... (t.l) Kl-H' fiii. A 7Vim Jmtrnnt sliced, and possibility of imittidctcr.lion, tlie bad indicated that it would be prepared i,, most siiiialdf ferlmiqiic is C!l/J. I is tensi- () provide facilities for ro-ordiuatiug ri.|. livily (in I lie nnungram range ivitli dir more hilnirnlivc studies of existing radinartivaii,.,, sensitive dcirctnrs) is approached only by mothnds, (6) ns*isl organisations in ||,e u,, l!ii* cholinesterase. inhibition procedure, and of activation tccliuiqncs for tlic cvahialji.i, * it. is immnlrhrd on the other counts. How of analytical methods in general, and tr, | ever, (here are two aspcris in the analysis help laboratories wishing to establish radi- I IDPAC Con of trares of diclilorvos by GIX7 in which chemical techniques (15). Il was' agreed ili.,i improvements are nreiled. These arc the sti[v- while radiochemical methods of analv-i. |lv II. EGAN, pression of dcenuiptisiiinn of diclilorvos on were useful for mercury and fur linnnm. wall Iliin.se, Slant the Gl.C rolmioi, and the selection of the residue determinations, tlicy were very r\. lest detector fiom (n) elorlron rapture, (h) pensive and not ncccssmily more, sensitive | The first meet thermionic, (r) inirrocoulomclric, and (d) more specific than some other nieilied- 1 Ann of the Pcstii flame photometric. Moreover, nlthougli they were often ier(nl I Chemistry Diviv The other sensitive method which is in in metabolic or field residue trial Mud*.. j (Viieva in Move widespread use (and which, together with radiochemical methods were in general in- ] ni.'insliip of Dr. J GI/C, oflcrs additional evidenre of identity) appropriate to regulatory methods of anali. | count, of the pi is the cholinesterase inhibition procedure. sis; the development of various other iiirtlmd- | minutes of the This is a general method for anticholinester of regulatory residue analysis was far mun ' |x;ilixcs drawn 1 ases; In analyse mixtures of inhibitors, suitable. incinltcrs of the 1 l separation lieforr the analysis is required. However, tlm volatility of diclilorvos is / IlrnaiKNcss 1. Trrtnin \ i such that it can lie steam distilled from ex tracts even when they contain a high pro portion of fatty material. It is possible, there *(1) Jensen and Widmnrk, Acta Chan. Sran-1 in press. , (2) Robinson, J., Richardson, A., and Kls.i. The commissi |Kisition rcgardii fore, to obtain a degree of specificity in the analysis for diclilorvos by cholinesterase in K. E., "Chemical Identity in Ultrainmi-- Annlysis," presented at tile 152nd Mn iwi of the termiii.il chilling earharyl, hibit inn by incorporating n steam distillation step before the determination. - of the Amcricnn Chcmirnl Sociely. S. jtcml>cr 1900, at New Vork City. linns behiw, and further this knu Procedures for tho collection of diclilorvos vapor from the air, extraction of residues (3) Bowninn, M. C., and Rcrtisn, Jl_ 7't.Journal 48, 013-052 (19G.11. (4) Laws, E. Q., nnd tVcIdcy, D. J, .-I/*( Card to the ns lirnductiuii. from crops and (issues, ami cleanup arc available. Diclilorvos may bo quantitatively 86,210-255 (1061). (fl) Salimnn, P. M., Annl. Client. 36, 113 III (a) J, riitimlirirt -- removed from air by bubbling through dis (1901). (tlimliin 11/ I'fiii, tilled water. Chloroform, methylene chloride, and benienc have been used to extract di- () Hughes, J. T., Analyst 88, 318-310 HOT' (7) Ceiger, M., nnd Kiircr, R,, Z. Anal RrifC Aihninixtra tt.C. 20201) chlorvos residues. Partitioning from an Chem. 174, 401-407 OOCO). In the rarlier : organic solvent into water, column chroma (8) Buchlcr, W., Ilcixlcr, W., and Filter. II liotli enrbnryl a tography tm-silica get, and steam distillation provide adequate .rlcnnnp from fatly and nonfntty materials. 7. Plperonyl Dili oxide Residue Analysis The Commission recognised the need for Aid. 213, 28-30 (1065). (0) Bun, Y.-P., nnd Johnson, E. It.. Thn Journal 46, 524-530 (1003). (10) Giang, P. A., and Hall, S. A., Annl. fVm* 23,1830-1834 (1051). (11) Ciang, P. Am Bmitli, F. F.t and Hull. S. A . J. Ayr. Food Chem. 4, 821-622 (1050. l-naplilbol, wenon. mnny crops > l-naphtliol waf arnte from rarba that 1-naphthol separately fruoi reliable met boils for residues of piperonyl (12) Porter, P. E, "Vapona Innerii.-i.!. enrbnryl cslahlb vr TRAN 056032 HARTOLDMONOO11115 St. Louis February 27, 1967 ^TKZT- BaxaWood BRUSSELS' Thank you for tha information you sent no. I am having our analytical people, ms wall as NCR here in tha statas, avaluata it. As far as tha toxicological part of hla report is conoamsd, he has confused and interchanged tha experience on chlorinated biphenyl, chlorinated naphthalene, and- a combination of both. This really la not too important, however, as there is no question but that Aroclor does possess a certain amount of toxicity. All our literature says this, but whether nanogram quantities mean anything is an entirely different matter. I think we should fight the battle of the analytical method first before we get too involved with toxicology. RKK/ln R. Emmet Kelly, M. D EXHIBIT COMPANY CONFIDENTIAL THAN 056A57 HARTOLDMONOO11116 I KractloiM Inn ton to 4 to * 1(1-* ltl 111 * III III III * Multiple* rsflx ipM n ii Ir* u multiple ........ hi 10' in* Hi* lt> 10" ts he teet/lrtetf at kuHi m poM Symbol (te* I.* k M Cl T Compound prcflxci sltould aol be ueod. Thu* 10-' moire it rrprraentcd by I nm, not 1 mpm- The attaching of a prefix to null In rffcct eojislitutos * now unit, to that t km' - I kin)' - 10*m* not I jt(jn') - 10*m*. Whero possible any numerical prefix ahould appear in the numerator of an expression. phyiictl quantity length volume IMK density fore* prawn l:>nm|>lr> '* till"" t '.'Hlirury lit HI, wlllt their Kqulvttlcuiv unit iiiixelruin ' ini'll Coil .Mini lililn tituitH*nf inilo v,|imr ini'll....... M|imrr> hurt u|uro ynril m|iinri* inilo ruliir inrli I'lilm*. font I'.K. gnllnn pmimi Splouugnd/ruble inch pound/ettbie fool dyne jitivndad iHiund-foree kilogrammo-foros atmosphere tort pound (f)/sq.ln. equivalent In ' in 011251 in it time in II IIIC4 in I-Moll .11 km I Xt.M m km....... nir.tn t,ii,,i n-tnt'j W13 in' IIK3II 127 III* , 1-riHti tnrkiM* 103H ?l x in m' 0-02M 31(1 X in' tl-tlO I cell <1112 0 CM AIIV 37 III K MM k* 8-W tMIX Ib'kqm' 180185 kg m* Ifo'N VltttM N t tm *J N tl 00 * N 101 m N m" N - IIH'li N m ' I i I Organochlorine Pesticides in Seals and Porpoises ! /' 4*n, w fttlll* 'I A' (ttf f|i*llfi\\A4 ti*j ii: ! f*<4>(|l`4 * r* itii niifil v i kril `Vl|r* Anti t\.r> r vMt>*r-lMti)i uilli rnixm Attlplmif' mi Iht'it mmiy* 1rchnf|i*. * I>/)K, Anil * initvsj, k/iI i ihf nri^mul nmi p,;''TD frum tho vo tn th HO pOHi' wlmro [iriiNM AfToci^l, A t>et-n iiieil to iiilerfrroittM1' s Tho priiin^ rxftmincd Hr in miirh t*m* lower corwvni ScottiKh lion* of all by A. V. HOLDEN K. MARSDEN rrnhwatcr Hthsrltt Lsborttor^ rttlothry, Pintnhirt Soli nd porpoise* In Scotlsnd nd Canid*. fir from the sites of ppllcitlon of pesticides, cm ccumu(te hljh concentntioru of residues In their blubber. These chemlcils ere spreading through the long food chain which ends with seals and porpoises and obvlousijr cannot be confined to their place of discharge. Tux province of orgiinochlorino mvii)in*u in marine life in harp soals {Phoca preenJandioa) on the Canadian Atlantis runny areas of the world, including tJin Antarct ic, has boon coast hove also boon examined and the result# of lhr reported rcci'Olly1''. In Uritiili witters the accumulation analyeos aro reported hore. Examination of samples of of n>idue in the egg* of sja birds' and the proooee of soal blubbor from othor ore** is continuing in order tu eonoentration of pesticides (through oortr-in food ohaina aeaoaa tbo variation botweon difforont rogions of the marine in the murine environment',hive boon xtudied. Analyee* environment. of varioue sporios of marine fish end mammal* from All tissue enmplo* from Scottish waters wore frorrn boottish water* during the p**l 6 year*''' have thown at -- 18* C until required for analysis. Tho Canadian that organochlorine rv.-t.uue*! are now a normal oopur- samples wore preecrvod in 10 per oent formalin, whirl rence, the highest oonoentrktloiis being found in organ* showed no evidenoo of any iiifluonoe oil the analytical or littur* with vho highotl lipid content. Thus the muscle prooodure, and in this and othor oases involving fish it vlutte of anlmouid*, the livers of ood and the blubber of has not affected the efficiency of recovery of posticiik' seal* act ns storage site* for t)io*o residues. residues. Aliquots of the samplrs (6 g) were ground to The aquatio mammal*, svjoh a* whalo*, seals and por- powder with anhydrous crystalline sodium sulphate (Alt poiact, have a relatively high proportion of the body weight grade) and extracted in a Soxhlct apparatus with re in Urn form of milxmUnooU*' fat (blubber). Sorvls food distilled Alt grndo n-hexono (previously levied and fivinil chiefly on g.uluiila nnd xolinolilijx, and chiofly on to bo froo of olectron-cnpturing mtiterini* by gos chrenve mall gndniil* nnd olnjiedid*. Tho process of onucputmtinii togmpliy). Tim hcxtvno extrarls wero mmlo up to lfkiml. of pesticide* through their food eluvin might bo cxposled und 26 ml. iiliqnoltt woro vubjocted to eluon-up In' to result in high pesticide Itivdl* in thnfal of thosomammnla. the hoxeno-dimethylformamirio partition mothod t>f dr end tnmplos analysod at this laboratory confirm this xpoolaiion. In reoent yesra, specimens of the grey seal {HaUcteeru* grypus), commtn seal (Pkooa vHulina) and porpoise (PKocatna phooatnk) have been sampled from Koubcrt Monndor n of.', followed by column clean-up using alumina containing 6 per oent water. The loss of posticido residues from fat extracts so treated is up to *0 per eonl, but. as is customary in pesticide tnaljwi. the ooasts of Soolland. Banipl4* of blubber wore available no correction has boon made for such (oases in the rvaul" for all the specimens exsmiqeti, and in a faw oaeoa other presented here. organs were alto a vailabls. As Well as reoognixed postioide The cleaned-up hexane extract* were analysed by go*- residua*, other electron-capturing subetanoes have boon liquid chromatography on a Varian 'Aerograph IW-IA detected bv gas-liquid olurornetography and, in order to instrument employing two glow columns t ft. long x i establish whoVhor such subetanoes are as widely distribut'd outer diameter. One column was pecked with `Chromoea the peetioides, bi bber ijarnplos from grey eeale and ' sorb Jf A WlDM08 80-100' mesh ooabed with 10 psx hy nonJiydr 26 per coot < (lAnncJmn nnd DDT povfitjnii, i bout |0 per < i 20 per cent in l int^rforcnco. I materiel being 1 vaJurt* in Table ferenoe, for only lyaod. Roaulbt l > nolicoftbly difTe \ oombinnd In Ta i I. COSCtTT** ia t Aa anil : t)T of ururW a T,, kotlnnii. AiluK iri!i(l9A.WMi I .N. ami W. MiiiUfitJ. adwlia*aliM(hlS' 4t >Mf.aranldpu\rr<.<a|r{ofAll.O-in) rt, - Canada, i(^r|Alrn la., )vr. and adnii araU IIM7I f'aiiaOa. Cntet Slaif* iIT., Ihiin atultdiiii eowitU.)lnsd(I.ft(fliTrt) ). . adtili ysarpoiwriM?) I*. Scollan*K aflitU rraol-(lM5. IM7: Coriteminotioii the east const of tAbordeen to thr 7 *0*1 and north . Seal pups from tin ing grounds contn adults from the set samples from tho J ffr ~ EX_H_I_B_I_T_NO TRAN 055945 HARTOLDMONOO11117 m* it of It of >u|h /Utl y intii three tM vf Or lu larlniron-n ad inn which ylirnl Uli i( ticiil*' l to n > (Alt h re found ron.uX' ii.l. p '> of ll-' >U III' lip tu nulii g"- s-sir i in. f pent p i'/H' ,'pP|I Milt,-,.,,,. <MI, (Ull (In* nUn*r willi ||i mniM* anpjNirl. nilliil Villi ,i (ht rt ' i i r ht ii-Hi t/a1-l ItlldriwllH'lHW. 'I'll*' 'i<i'i*ii li*ni|**ril urn hiph 1X1" I itinpMi gi How AO m.....l../min mill I In* rnlnmii h*Milii`Uui f,r rfh+IrMi li-nt jilni] JI .IHNI tlM'orvliriil (iliilr*. VlMrt m no rp^nilifimt tl,'urrtil,ilimi of I)IJT mi tlm iiiIiiiiiiim. While rtmi|4i*ti* '|>n(nt inn nr llm nmminn |MwHnliln e'rilliii'H i* |nwilili* inj pin* nr ntlier iif flii`Mv,niliiii>iir, j,,li-rl,-ivu*v Ity jH*tyi-l*tormn1ml tii|*tn*nyl (IV1I) fi'Midln'*'.1 iiilli /i./i'TI)K nml li./i 'l/DT jx-fiUi* mxvxxilntoil n further timlylirnl nlnp*. Ali<)ifotii (A ml.) nt mmi* ,f tlm nxlrart* urn* i*i'ii|Hirnirtl to ilryWwi in n xlrvmn of mill filtered air. ml lln* nviiinc. rvllilxpd with ml. of -6 por coni .IcoIhiIic imlikuinm hiilroxklr for IA min on ft worm aatPT-Ixilti. All IT rnnjiiig, A nil. of iilirxiiin* wn* milled, tlli mixing. fiillniiril liv 40 ml. ,,r X jh-i- rent eniliiiin milplmli* w4ttli,iii. 'll,,.; Hil|x'rimle,il J,,-y,,uu Inycr wita llieii mmlymil liy *!nn li||llHl i'limiilii(ni/rii|i|py. |ly Him i<vliiiii|in*. t|ii,mlUlivj- jiHnvrxinn nf I)l>T In /p./i'. 1I)K. mnl nf p.p'-TIlk (to p,;'-Ml>K ( > 1IUMU), in ob tained. ftinl ( lie couvonjioU product* confirm 1110 identity of ihr original mvidiira. The re.idu*l jwxlii in the p.p'-DDT and p.p'-TDE poaitlonfi Where proeciit. can be aublracled from the veluoe of tho Iprelioide. originally determined in there poeitiom. Hyarplyvla nleo doatroy. a ondy-BHC, xliorc proeonl, but polychlorinated biphenyl. are un affected. A eyonoail eono (A i-60) column1* haa also Iktii ued to arparntc ,p`-DDT end p.p'-TDE from PCB interference, confimrin [ (ho Iftttor. TI10 principal poxlirido roaiduea fmmd in ell aemploe 'xamined eon* (Itoao of tho DDT group, with dioidrin 111 much amnller qttm t it ion. Canadian noela contained Inmrr oonmitrelion n fjioUlrin (linn Beiitliah nonla, while Sootlixli |Kirpnl*c onn .a(uod remarkably high eonoontrn- noiM of oil pel ieide rreidne. (aoo Table 1). Interference on I he DC-SOO *iliconoroltjnrut in thop.p'-TDE position ceueed by a iion-hytlrolyafthlo r viduo war roapon.iblo for about II per rent or tlie ^oaI oatimuted p.p'-TDE in tho Canadian nml Boottiali empire examined. In tlio p.p'- DD'l* poaithiu, the non-tyilrolyanblo maidno conalitiilcil about 10 per oeut in;the Cumulinn amnplea and about 10 per eonl in tho 8po{.llh aamplrw examined for thia yiterferonee, the total amount of non-hydro)yaahlo material being .mailer tn tho Canadian anmplea. The raluea In Table I have ijiot been oorreotcd for thia Inter- ferrnoe, for only a proportion of tho aamplea were hydrolyaed. Reaulta from the1 varloua apooiea of eoala were not noticeably different i^> ( given area, and bava been tombined in Table 1. Trblr 1. eoaciXTiiiiox ximiu or oaotxooatoaixa aaarpm lx rat or tana axe roxrouu (e.r.m.) IUmm In MnaUiMiwI Am anil Ko.la t)T* C. VittUnil, fttluU h-*U (IMj-M) S.lmrt V, KAritanJ, X *6.1 W. RcMUnrt, 1**1 pwm ritA, Ik., )ov. ftOuH m) lW> - * 1*6*4*.C*b(H It-1H T<M> ftoOmfVt*i^rrr-iHT) . *rfli it-U U1*7 mu CoiitruTvinai ion by ticidft It prater in Ihe ao&lt on tlir Mat oo*mV of Boot! (t*kon in an aro* roughly from Altordorn to ih Ty MLuary) than in speoimena from tha aftd north ooaata. inoluding tho Orhnoy Iil&nda. orol pupa from tho OrVnoy and Karri* (vrMt oooat] brood- ,ftt ground oonwiinod holy alightly lowor roaiduea than adulm from tho aama iroaa. By ooropariaon, tho Canadian tamploa from the Maftclalan laUnda (Gulf of Bt. Lawrano#) \rry |mw Icvrli ! I*.||| rlnliliiM mi1 llir i*lT \ilnlr (m'iiI* Immm I.! SIhhIm ((inll <l Si. 1^11111*111*1*) < I*miM |if|e|rM IhiI |h|.|i. tilr HMiiiliir lM I!**** fl StiAllinli n mIii. Ill lln* |\V *ailllilM`lie lhl IlMlM Of ltlM'y Hil-I I III. Il-llhl 11 iiiiiiittml, lit lln* lhn Inkm on Dm* i*mmI i**uih1- ii| HcmIIiiimI IiimI mnrkiilly hnl*'r r*li**l* f mII llir* MinMiinil. fhm M|M*f*MiH*ii Miiilnii*i4l 11 Ciilnl n*Mii|in* imm. milniliMM nml J>I>T if 7!i H p.p.m. Aimlynoft of a fvw tiKNin* oI-Imt Ihnn llm hluliU r lmv\ 1**011 inmii*. but crmixilrlivnN in Uo MuhU r Imvi* alwny Ihh-ii fmmd to l>o tlio highoat fjablo X). Connrtifmlimi in other tiaouoa aorm likely to bo ronaialrnt with Ihi ir lower lipid oontonti. IClflrf'rTy a*n!i \ltry*rm\ Orrr *r*l Orrr Ml FvtpAlW mM> out Of>KnTAATMthfl (f.p.lH.) 1 VArv ' IIHHMnliddwwrr UUrrff hhrf**l KKMM*n**|rr fRt|p>klf***K* lift Pt IVTT V-M fOt-tlfft, .. U* ft 4 0-ft7 < 01* 0-11 --* IS CM> H Oil 0 07 001 II oii peri 0-04 0 10 hwl* Tho proportiot% of blubber oxlraotable by hoxaiio uoi detanniiiod for aomo aampleOe Value* rangod from 72 to 80 por omit (moan 80 par cent) for tho Canadian leala, and from 88 to V8 )>or cont (moan 03 par cent) for Bcottiah oata aoxnplnt on tho brooding ground* off tho weat eoaat. (Vahioa for othor ar.al aamplea were not Mtimatcct.) Con* oontrntiona of pcaticidoa in term* of oxtraclablo fat for thoao aamploa would thu bo up to 40 per oent grootrr t han tho vivhioa in Tablo I, but iho gonrral compnriaon i not aigniflcAiilly affoolod. Tho lower rxtractable hit value for tho Cnundinn sample* may poaaibly bo a irault of leing prenerx'od in formalin. Conoontrationa of posticide. roaldnc* in the extractable fat of various organ* and tiwM of one porpoi*c hnw nit iin(Mr(4iiit miiitlon*hip (Table 3). While thu cunncntru* tion* of tho DDT group hi the original (iemic* vary widely, thoAO oxpro**od in term* of oxtmclublo flit art' in much oloerr ognif>mrnt with Uk> aolo exception of ilia brain, A similar anomaly for tiasim* of trout was described by Holdon11. It eoems likely that a largo proportion of tlio lipid fraotion of the brain may not oontain pesticide*, and tho brain lipid composition la known to differ considerably from that of depot fat. Tabk I, COXCISTKtTIOXI Sf TCTU W (p.P TM ) IX TIMCM Of A fOXTOUS Ttues er area* Bhibbsr Urn Iptos* 8/*la Coaeeairailan I* tl**w li ow o-t* 0-11 004 oot PrmrnUf* catrael- 170 11 11 3 11 14 1 S 0*KhDV*nf*tal tlM I* It It 41 t 4 II 817 (R^tolili f*t Th. nnidontiflod peak* on Mio ehromatogrumx M-nnn to be imilar to thorn produced by polychlorinated bi phenyl* and. to *.:abl* oomparixon to Itc madr. Ike rxtin. (Ri) of the retoittinu time* f all regularly ooeurring poek, (relative (o Hieldrin- 100) h*ve been calculated for the n|erating -column temperature of 00* C, lhco value* boing tompnraliire-dependent. Tho Rr value* of l'CM com|>oundR from oommerci*! PCB formulation" won- *)eo dotorrninod for bolh type* of oolumn (Table 4). A( len.t oeven J'CB-typo peak* were found, inrluding tho*o which iutorforo with p.p'-TDE and p,p'-DDT. Hept*chlor rpoxido and p,p'-MDE could not be confirmed on both eolumn* and are not therefore recorded. _ The moat aignifioant a*peet of the reaulta ia that, although aoal and porpoiaea inhabit an environment f*r removed from the aitc of application or diacliarge of poeticidee, they can oontain much greater concentration, of dieIdrill ana DDT group rcidue. than thoeo rooordrd for moat other specie., inoluding man. Robineon and Hunter11 found a mean concentration of dioidrin of 0-2 p.p.m. (rang* 0-10-0-7I p.p.m.) and a mean total eon- TRAN 055946 HARTOLDMONOO11118 ivnltutimi i|' |)|>T of 4 1> jt.p.m. (rungo l-U-H'J p.p.m.) in ntii|>lr of human jlvpt fiit iti Kn^lnnd in iO(U. Ku pviili'iw nf any .igulfVMilt tlMiigo na f.m.sd liming lUO'-'-Od. 1 Tw 4. wmm imMi Win (Jl>) or awuieuiu (iiutmir - io) /TWO coin HcMn> DC-n0fQr>i eolcam IVH - le t TV It f.^.TUK rW*l,,nT n*H Pci 131 -IIWlA - 170 IT4 SOI 9*2 m II i *>. . rcn rI.l>rie.'-UTMrU)lI*a ----111nH01<0 i- tII-TVr'-IIIOI O.T --I4ISt*-t -147 rvo - t*4 res -tat n * 100 Itl in HT Ml IT* The rnl* ond porpo nifo from tho mmI couai of Hootlend \vor<< utiinlly mill'll eMoutly contaminated than those from tin- north and wM. ooaola. Thin, nl lout in rotpocf nf nonlii. moy txs bet-amp, m ii boliovod, tho population* in tin- lmo nrnmi rnmo from difforont brooding allot. Tho onk miitli of AImtOiW brood prinoipcdly on the Ftrnr lulumill, off till- north-okeit oonoi of England, while the eal. of north mid wnkl-Scotland are primarily from tho hreeiling ground# of kho Orknoy Ialando in the north, mid ollirr itlnndt off tW wett ooaol of Soolland. The ora off rattorn Sootltnd it alto likoly to reooive more oon* lamination from ettiu ri le ditchergot than that ofT north und wont Scotland. Similarly, the two aeparato aoal population* tnmplod ;ff the oaat Ooatt of Canada may inhabit emit with diffrrAnt level* of contamination. Pup* contain pctlioide retit up* in oonorntration* only alightly lower than in the patent population. Common noait in Holland have boon fo.irn with ronoentrat iont of n<iidno tlmilar to those of eetlU on the Soottith oaat oonet ". While tho rutldue oojioontration# in tubcutancout fat ore high, thoeo of otljtf liteuee and organ* tro found to bo much lower. Thit tuggoala that thore it no riak of pltytiologioal effect#, Weet the metaboliam of much of the fel in limoe of lUw ieedt to a eontidentble inoreeae In the oonoeiilretlon pf the reeidue in oiroufating lipidt, end thn# in reeidue leonoentrationi in other organ* or Uteuee. * (iroy msmiIm iii iIm uuiimi ii( ll*> SciMili iti/iHtliiiitl priiimnly nil Heilnmii {Sidmn aninr) und rml ftimlna Ttutrrhlint'*. 'rim ingleueil- 1-iiiii-iMitriil.iiuiM nf JN^l.icnli- i,, nnlliHiiiidM in tine iimriieit oiiviriiutni-nl imvo an fur ln, found in hou i rout (.V, fru/ln) on llm uiHt reuwl with up p, 0-i p.p.m. (ilii-IUrin -t total DDT) in motclo lim.im11, atui ealmon from litre autito unut woulel proltably lutvie Mmilnr oontonta. Cod exrtminnd from tho wt eoruil havo oon. lainod op to 0-3/e p.p.m. (eiie iilriei + into! DDT) in inntr-le, lietetiiet fntiwm 0*12 p.p.m.) eeeeel from tleo weieit eoetnt tep le, (I'M p.p.m. (ntoan 0-22 p.p.m.). wliiir oid livnm remleiin"et up to 4'0 p.p.m. and 12-0 p.p.m., rewpewlivoly. limy wela arc reeliinntud to nut abeeiil Ifi Ih. of food Unity, iit,d lienee nn adult aoal oouid oontuiim ite own weight in food in So So day*. Aettuming e high proportion of the poaticiilo intake, to be ttorod in body fat ralhor than to bo nxcrutod nr mctuleoliiod. an incroaae of two ordure of magnitude in poatloido oonoontratlon from food to body fat within t Fow year* it feeulble. Thit degree of accumulation ef roaiduo in an environment not deliberately contaminated, and in apoolea ooologioeily far ditlant from tier target orgaieinm* of pereittent peelioidc*. underline* the impoenibilily of oonAnlng eueh ohemioal* to tho aroe* nf application. We thank Dr B. B. Roe for obtaining tho Bootti.li eamploe, and Dr C. J. Krrewill for tho Canadian tompb-,. *Melel Deo.eeib.1 t*. IMT. /(/*. rwliinr'i Xrl. Adi. Ctena. IUt 0**1. Fried)** OBm. WwMrU. IOC)). T.tlon, J. O'O.. *eid JnuM*. J. It. A., .Value*. Ml. #41 (IttTI. Moon, )4. \T,, tad Tattoa. 4. O'O.. Wvr,*W. 4t tltdt). AoUowe, J.. glehardtnn. A.. Cretan*. A. N.. CouIm*. i. C.. tad r*Ue, (I. II.. Jrrn.U4. ItOI (IM7I. Pri-rleo**! of Atelreellort aed fitherlM for Soollaed. rithtrira tf Mland. Itororl for ltd*. D*tarta.nt of Airkullon aed nhrto* for teolhnd, n*hrrm f tntUnd. Orpon lor lttd. ' p. r**h*rt MnuniUr. W. 1.. tUaa. Oo.ll). E. Vf.. M*aiad. *. W. Outrun, aed TIkmmod.7;. Aim/fit. t, IM <itt4). />. #., Xrw OrlrMM. td. tit OMdl. Holmtt, D. C,, lliamow.4. H.,t*d Tttton.h O'fl., Jfalw..t)*, It) (1M7*, '* Slremoet, J. H.,aid Tattot. 1. O'O.. J. CAnm**.. tT, tU <IM7). Hold.*, A. v,, Awe. Aral. *Uf,, %. t tlttt). " Itoblatoa. I.. Ill Mutar, C. 0.. An*, tmrlmi. B--UA, U, 144 (Itttt Koomta, i. H.. aad *ne Otadtnt. H-. J. And. M., I ft*r#*.), * 0**4t Bar. . Mar. Bu.. w. 1. tt UMOV . * Bold.*, A. V,, J. iffl. M.. OMdl. ' ,I The North Raclfic: an Example of Tectonics on a Sphere | *>r I D. P. HcKENZIE 1 R- L. PARKER Iftitituit of Gaophn'a tad Pitntury Phytici. (Jnlvtnitjr of California it IStn Dlt|e Individual ueltmlc area* move w rigid plttei on the surface of t Sphere. Application of the Mercator projection to slip vector! showi that the paving stone theorp of world tectonics Is correct and sppllti to about a quarter of the Earth's surface. r Tub linoi'r mngmitto *upmiiliea,-> which panvllol all aotivo ridgot ean only bo proauood by revorenli of tho Earth** mngnetio field1 If the oeeanio orutt it formed oloee to tho ridge exit*. Model*' have thown that the anomalio* cannot bo obtorvod |n the North Allaiilio tiniett moot dyke intrution, and honoo oruatal production, occur* within 6 km of tho i|djp axil. The epmoding *ea floor* then oerrie* thoeo encrnialie* for groat horiaontal dietonoee with little If any defprtnaiion. The cpioenlree of earth- quaked also aoourotalr follow the ax it and are offeol with it by trannform faulu*-*. Th* ttruolure of island arc* is Im door, though the narrow band of shallow earthquake* uggoeft that orutt U jeonsumad along a linear feature. Timer oLmcrvutiunt aro uxplainrd if tho toe Amir Hprvnile us a rigid plate, and intoraote with olhor plains in eri.- micelly active region# whioh alto thow rooent tectorn, activity. Kor tho purpoeo* of this artieln, rldgo* Md tronoho* arc rctpoofivnly dofmod at lino# along whk-k orutt it prodnood and drtlroycd. Tleey need not alto hr to|>ographie foauire*. Trantform fnultt conacrve en* and are lino* of pure slip. Thoy ore a]way# parallel, therrfoce, to tlie relative velooity vector between two pletc*-* moat useful property. Wa have tested Ihl* paving ttonr theory of world teotoale* in the North Peteme. whwe u work* well. Lea* detailed ttudiea of other region* *1* support the theory. , Kit ri. oemiev can r on a carTitaxia (I lion. I ion . n lot lot about llte-d : A( (it.it iiiiii'rn wnno |i biilweo MllVlil c that pc lino eef the Ii). ti oncli l Neither Crust, tninll ci Thin nri useful ii, oonsev|ier OOruwe t rooeoii v along ic rotation* not do * no tignif tion )iin eon't* ct motion* i tionel liy aaeitmic t turfaro of Thorp of tho Ki At such ; tho jiliifti boTiiuoe, g tho third methoel it Utan on i from the f from a po w-iee, tho . the dirocti Similarly **. are ref vector dn oirouit ret TRAN 055947 HARTOLDMONOO11119 H II *!* . TO T* r- MiJi i'ttj<}3f..,lar>afla___: 23rd Tibruary. :96a Arcolors DVW^-JS v.|t, lucliard, lit, Louis FEB 266119966i k A - c r.d tv, Sruaseie kuabon . it* Louisa >-7 C.uttny it. louts it. Louis St. Louis Ulth raferonca to your lattar to Dr. Bartar vs not* that yowr available <iuaatitles or <li- and txiehloroblphanyl isowors nrt vary snail indaod. i.t . .ou know v hart already provided maples for Jenson and Wlbrk (Ktookholn), itLohordson (Shall, England) sod fatten (Covaxmant laboratory, England,, L\d Ui* rnoidual quontltlaa nro new to in rookonad In tares ct Hillioraea. a osouma you will bo writing appropriately to tha LyracuatOnlvsralty iUsserch corporation. Oa your request for Information coneamlng tha tasta udo by tha stove wumra on our taaploa I oan aunaarlso aa follovsi* , (a) Janaan-andl Vldwark I havs asm no dsvalopaant slnoa vidaaxk'a lotia* of Voferuary 27 th 1967 andreoasd to Cana Wild*. ^ : (b) Tattoo C'Opiaa at a paper entitled ' Uilerinatsd Jlydxeearbona In British ' Wildlife1 by D.c, -'toLift**, J.II. -isnone and J.O'G. 'Ihtton. Batura Vol 216, Oot 71, 19217 pp. '-.'27'279 vara pasoo* to Maaava. Vilda and Duaharan with Kf lattar of 4th Novawbar, 1967. This paper eonTinss tha work or Janaan d in particular shews closs uiailarlty betwean gaa-iituid ohsosatoeraas of (s) artrwta or Keatxei livar oil and (b) a eoaMrcisl polychloroblpbanyl resin. (o) Richardson fciohordoon has rot pubiiohad anything ao far, but J. ifcbireon, also of U|pli iiURoareh Ltd,* Tunstail laboratory, lilttlngbouras, Kent hua published a papor entitled 1 Htalduas of Urotnooh1orioe fncectioidee in Birds in the Units! i.lnrpos, Chemistry uut Irvlustsjr 1V47, pp, This to s curn(rfoitani.lv* oviav but ao far ou i cm so it doaa not sugjait that any of tha rouldues oontuin chlorinated polyphenyla. a However, i was in corroopendonca with Richardaon in llovonber, 1967 (copies herewith) which atiowad that ha uaa rutlefled tha* ootoohlorobiphenyl was rr.Jnt and that his raaults ora aubotontlolly in lino with thoas of Tatton at al. You. will itotu also that ho baliaves thut the contahicbtlun of bird Ufa la in th* vallay of our hivar VItha*. . I liavt judlnloucly followed up thin olu* with a view to locating tha ootres of tha onAtunlnakioni thsra appeuro to ba no opnrution of any lisa involving AMoloro within ilia withasi vahty. The naarast is at Xlitga Ljrd with uiors ror AlaoUrteal ^ruoneii. A* HCIl r> .wento tna rrcutssfc off-tabs or Araclor and un them la 11 /sly to bo at leant ;-*a -oita*c in tha proosca 7 ausplelori la that it lc aittiov in waking NCi or poauibly in dealing with tha oaxap that t)<* oontdnlnation ariusa, . . .... ......................................................... . . . _- 2 So tur th*ro la nu indloatloo tluU tha Public Author!tisa aza'worrlad. .. ro;,?MlY COM?pE-mw-.. D.V, .. ,'A.iST ' TRAN OBfcOH PLAIN TIFF'S ^ exhibit m_44-^ HARTOLDMON0011120 D.Y.H, Hardy, London 2Jrd Pabruaxy, 1966 Aroclorg ' wsa/ss W.K. Richard, St, laula J.V. Soxratt D. Wood R.A. Butts H.E. Xally R- Kalla* C, Paten . Parlca G. Vilda London BroMala fcaaboa St. Ionia J.F. Qu*ny St. Louis St. Louit St. Louis Vlth rsfaranca to tout latter to Sr. Baxter v* not* that tout srallabla qaantltlas of di- and fcrlahlanobipbsRyl laeoaro an vary anall lsd*d. At you kamt w* hmrm airway prorldad sasplaa for JantaU and VtAuak (Gtoekhola), Hiahordson (Shall, Sogland) and Sattcm (Cwnaanant laboratory, filmland), and tha residual quantities an am to b* reckoned la tana of alHignaa. Wt atvuM you vill be writing appropriately to tha SyraoanalTaiVMraity Beaaanh Corporation. On your re<ju*ri for Infoxsatlon concerning tha taata aada by tha above woxtoxa an our saoplsa X aan sumaarlso aa follows1- . (a) Janaan and Vldnaric X have seen no devalopaant alnea Wldnaric'a latter of Tsbruary 27th 1967 addxsaaad to Cana Hilda. (b) Thtton Copl*a of a papa* antltlad 'Chlorinated Hydrocarbon In Bsitlah Vlidllfa' by O.C. Koines, J.H. Slaoooa and J.Q'G. Batten, Hater* Yd 218. Oct 21, 1987 PP* 227-229 vara paaaad te Mass**. Wild* and Buohanaa with. cgr lattar of 4th. Hovauher* 1967. Thia paper confirms tha rock of Jensen and in particular shews oloM ainllarity between jae-liquid ehroastegsas& of (a) axtnurte of laatral live* oil and (b) a eeoaerelal pelyatalorobipbaaarl xeela. (a) Bichardsoa Btahezdsan haa not pebllaheA anything *a far, but J. tefolnaon, also of Stall Rtssaroh Ltd., Tun*tall Laboratory, sittlfl^bourm, Xsat ha* P'xbliahad a paper antltlad 'Baelduas of Orcansehlerine Insecticides in Bead Birds la tha Baited Kingian, Cteniatry and Znduatcy 1967* PP* 19741986. This is a eeeprehsnalv* raviaw but an far aa I can aaa it dots not suggest that any of tha residues cantain shZoglaated polyphasy!*. gftwiim, I was In eoKxaapcndaaM with Eiohaxdsoo In Hovsebsr, 1987 (ooplaa herewith) wMeh Showed that ha wee satisfied that oetoohlorobipheayl war prassnt and that bia raeulte aaa substantially in lint with than* of Batten at al. You will note also teat te believes that tha eonterination of bird Ufa la ia tha allay of oar Elver Witten. 1 hava Judiciously followed up thla alua with a virw to locating tha aousca of tha ocetsainaticni these appear* to ba no operation of any else larolviajf Arosloce within tha Wlthaa va3ay. 73* nearest ia at Kiajp Xy*n with eaaae for alactrlsal purposes. Aa VCH rapraaanta tha flattest off-taka of iroalor and at tear* la lllealy te ba at laaat ion wastage la tte proaaaa or auapiclca la that It la either la -asking ITCH or possibly in dealing with, tha aozap that tha acntenlnation aciMa, ' So, far' thara is no indloatlon that tha Fublio Author!tias ara worried. COMPANY v was. CONFIDENTIAL TAH 066030 m HARTOLDMONOO11121 I i Monsanto r*OM (nauk ft location) C.R. COLEMAN - Ruabon 'S/w tJwM. 2/ Y DATE ' tUftJCCT 11th June, 1968. PYROCLOR DISPOSAL - Your memo 30.5.68. P,J,A. Marsh - London D. Wood - Brussels RCmCNCff crc/emh TO J.M.H. THOMSON - London The only reference that I have to the pollution of the atrecsphere and rivers by chlorinated diphenyl is New Scientist, 15 Dec 1966, p.6l2. I do not have any of the original papers by Or. Jensen, I would suggest that you contact Dr. Hardy who deals with toxicity questions* and was directly involved. . COLIN R. COLEMAN TRAN 058004 a 34 HARTOLDMONOO11122 E. Scott Tucker Applied Science# Section - RtcD Laboratories January 30* 1969 CHLORINATED BIPHENYL IN Wlt-DUFE R.. E. Keller W. R. Richard E V;heeler Dave Wood Brussels, Bslegium Ff- Would you please bring us up to data on chlorinated hiphanyl in wildlife. More activity la going on la the States. We have eome analytical work and acme biological work under way to aee If Aroclor la really present. Has Baeyer. Progll and Kuhlmaa done any identification work? Has Jenaen confirmed hie initial publication? What chlorinated hiphanyl laomera did we actually supply Jensen? Did Jensen ever forward any more analytical data or details to you? E. Scott Tucker atEXHIBIT NO. HARTOLDMONOO11123 Monsanto rnou <Nu< location) DATt *U4CCT RirtMNCl TO : D. Wood - Brussels 4th February, 1969. m *" * Chlorinated Biphenyl in Wildlif-. DW/ec . cc R.E. Keller W.R. Richard E.Wheeler - St. Louis - St. Louis - St. Louis E.Scott Tucker - Applied Sciences Section, R & D Laboratories, St.Louis. J Thank you for your memo dated January 30th. At the time that Jensen in Sweden first published his assert ions about the presence of Aroclor in wild life we met with him and discussed his work. As a result of these discussions he admitted that possibly some of his conclus ions regarding the hazards associated with the chlorinated biphenyl that he had found were publicized out of proport ion. I don't think at that time we questioned that he had in actual fact found chlorinated biphenyl in the sea eagles' livers but questioned his incorrect quotation of certain medical information. Since he had appreciated this point we then let the. matter rest, not wanting to stir up further agitation in other countries. There has been little more happening in Europe until about a month ago, when an article appeared in a Danish newspaper disouss- ing Jensen's work. We are trying to find out at the present time Whether this covers new work or whether it is merely a re-hash of his original paper. At such time as we get any further data we shall certainly let you have this. x Best wishes, (N S1 TRAN 058495 HARTOLDMONOO11124 Monsanto u toe.T.o-i E. P. Wheeler - Medical Dept. PAtC WPJCCT ncrciUNet TO April 16, 1969 POLYCHLORINATED BIPHENYLS IN THE ENVIRONMENT R. E. Soden - Brussels CCi J. W. Barrett - London D. N. V. Hardy - London R. A'. Baxter - Ruabon H. R. Newman - Newport ......D...Wood " Brussels ~ J. Haggert - Brussels W. R. Richard R. E. Keller R. E. Kelly Perhaps you have heard that Bob Keller from Organic Research and I plan to visit a number of people In Great Britain, Sweden, the Netherlands and Germany concerning the recent nation. f.~polyhlorlnated biphenyls in wildlife tissues In various parts of Europe and the United States. Your people in Europe were the original contacts in late 1966 and early 1967 with scientists In university Bnd government laboratories who identified PCBs as interfering substances when determining chlorinated pesticide residues In fish, sea eagles, pine needles, etc. During 1967 and 1968 there were brief comments in the U.S. technical and trade journals concerning the PCBs but hot until February of this year did the story break in the public press (see enclosures). Beginning in mid-summer of last year a considerable research effort has been underway in the Organic Division and in consulting laboratories to develop data to protect the sales and uses of our PCBs. It has been concluded that before committing even greater expenditures, we should determine what efforts are underway by those people who have been in contact with Monsanto requesting samples of our Aroclors, reporting findings and mentioning specific continuing analytical and toxicological research. I have enclosed a list of the individuals Bob Keller and I hope to call on and an itinerary which is farily definite at this point. Dr. Barrett haB been most helpful in arranging for our visits in Great Britain. We in St. Louis have made direct contacts with the scientists in Sweden and in Amsterdam and I hope Dave Wood or otherB in your . group will advise us as to whom we should see in Beyer at Leverkusen. There is general agreement here that it .... would be desirable to determine whether or not Beyer is as concerned about the potential problems for the marketing of polychlorinated biphenyls and whether or not they have equivalent research efforts underway. I believe Dr. Kelly went into this subject in some detail with Dave Wood but he is not sure that he discussed it at length with you last month. EPW:cJs Enclosures ^l Elmer P/ `Wheeler tran 058769 HARTOLDMONOO11125 ft.P.V. TOP. RUABOX 8th faptonbar* 198?* fAXTOTHKKM R,nnc/BN T.J. HSBjOUPOSSK, BRUSSELS D. Vood2/'Pr^tti#Xa , D.T.W. tondon ^ KiR KttMB) Kiv^ort to M* Tour nan* to Dour* Brd]r ho* boon rafarrad Poug 1* m holiday. I pmum that tho quary fron M. Sohultawa of tho Kaguodoas not rofor to Santothorn 130 or 190 a* tb* Aroolor hooklot Is nontlonad. although of eours* thoy vould ho orach abro Irritant to akin than tho Aroelors. Tho ehlorinatod diphenyls aro not noraally associated with akin irritation although thoy oould da-fat tb# tissue* and |1to riso to tho "aolront" typ* #r Mcia luim. This h(14 bo troatad with a lanolin* based craw, possibly in eonjuaetlon with a stereid, at tha diserotion of tho aodieal practitioner. Tharo la wary llttlo infomat ton in M. Sohultena1 a nata a* to how tho gantotham la bains handlod and what ita us* 1* in eoanaatlon with tha V-kerk ahipaf but It in wary inportant that tha aroelora should not ho in oontaat with akin baaauaa thoy nay ho abaorbod through it and ayataniaally thoy eon ho lirer poisons. Z7//- 4/t,/ EXHIBIT N0.dl2 l( hr A, (fltt fr p.F.w. m - TRAN 05801k HARTOLDMONOO11126 ..'.v,?.sar i$t Louis Qenoral Offloa* ,, C \ fr Manoh ^25# 1963 ^.Theref^i/Pflantotherm Contamination of * Cooking Oil - Smith Potato Crisps#.... ..7 Holland ----------- -------------------------------------------------- P, Vood * .BRUSSELS scions 1700 & S. Camoron - PRUSSEIB M. Echuitona - tt: *!.;oue r53T7tawiWr*a53a^^ HTJ/ilD/SS .......... ................ ..................... T. Penton-Roberto - LO'IDON Pave# I have eiffixed copies of two reports from Pr, Keller's croup on subject cooking oil contamination. The latest memo dated tfarch 7# indicates that there in lean than 20 parts per nil lion Thomlnol/r-antotherm FR-1 In the used peanut oil. Also indicated is the need for more sensitive measurements# which will be made <*hen the analytical * equipment lias been repaired. . . . _ Pr. Keller *o group is cognizant of the problem ve have with chlorinated biphenyl contamination in the food processing industry and have been doing a fine Job with thin very difficult analytical problem. I shall notify you of further'developments in tills area when the information Is available. Best regards. >* ,.'V. 1 k : r . ERilh Attach. . Pen Roush COMPANY CONFIDENTIAL tran 057507 HARTOLDMONOO11127 1 Monsanto '** %...* . too.TM., C.H. COLEMAN - Ruabon 3ari BuftJCCT OTMNCI ^ 5th August. 1968 PHOS^J^ranu DECOMPOSITION OF... ^ I^ANSFORMEHjASKAHEL ^ v CBC/EMH TO : P.G. HEJIGNUS - St. Louia ---------------------- D. Wood - Brussels J.k.M. Thomson - London R.H. Hunch - St. Louis A prospective user of transformer askaral has drawn y attention to the book 'Transformer Engineering1 by L.F. Bluaa, A. Boyajian, G. Camilli, T.C. Lennox, S. Minneci, V.M. Monts lag*r, all of Ganaral Elactric Coapany, Pittafiald, k'aas. (John Wiley & Sonaf Inc., Now York, 1931). On page ky* thara ia a tabla of tha decomposition prodncta of tranaformar askaral - showing that 0.01% of phosggna ia prodacad in an electric arc through ' air-saturated askaral at 25C. It was aoat disturbing to coaa across this information, particularly in a book publiahad by G.E. paraonnal, sines this ia a variance with raporta publiahad in Franca and Germany, in addition to our own publications. . For comparison, I giro tha coeq>lete tabla from this book together with 2 other sources on tha subject:- Gas G.E. Book Clark* Monsanto 'Black Bo HC1 97.50% 2 Unsaturatsd hydrocarbons 0.60 - C02 . CO 0.28 0.28 Phosgene - ..................... ..... 0.01 Saturated hydrocarbons - H2 C12 Inert (N2) 1.33 97.0 0.25 0.50 0 0.25 ....... 0 0 2.0 97.3 0.6 0.3 0.3 1.5 100.0 100.0 100.0 * PA .MJg.* Clark, 'NnVoUnAfAlaMxnBawbalev Vo4rg|aMn*ic compounds' ; Ind. Eng. Chen., Vol. 29 (June 1937) pp. 689-702. BIR 002173 O 6296O64 HARTOLDMONOO11128 2 The following investigators have aought phoagena but failed to find it: P. Jay, 'Etuda da la formation da phosg'ene par decomposition dana l'arc electrique daa hydrocarburea chlorea1; Chimxe at Industrie, Vol. 92, So. 5 (November 1964). Anon, 'Opinion on tha behaviour of clophena in thermic and electrical treatment1; Report from Chemisch-Technische Raichanatalt, Berlin, 21 Kay 1940, Register So. 176/40C. Both thaaa inveatigationa used aniline-water saturated with diphenyl urea for detecting the presence of phoagena. I am not an expert in analytical methoda and wonder if thia method ia sufficiently sensitive to detect 0.0l of phosgene among the other decomposition products.* Perhaps another investigation using sensitive physical methoda of analysis would be worthwhile, particularly if it could be scrutinized by an impartial observer, from some official organization. Any background information that you can give us on thia topic and thia G.E. book and its authors would be very welcome. See you in September when you visit U.E. . Regards, COLIN R. COLEMAN * I hear that there ia a colorimetric method sensitive below 100 ppm. 6IR C02174 o 6^960 6:j HARTOLDMONOO11129 MONSANTO CHEMICALS LIMITED <f V *tC'eS MAY 15 1969 PRODUCT TOXICOLOGY f- AROCLORS^ Report summarising present knowledge concerning chlorine-containing residues in wild life and visits made to organisation implicated therewith during the period April 28th - May 1st, 1969. by: D.V.N. Hardy* Clrculation 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. Herefousse, Brussels. D. Wood, Brussels. R.E. 5~pdt. E. W.R. H.S. Keller, St. Louis. Wheeler , st . Louis. Kelly, St. Louis. Richard , St . Louis. Bergen, St. Louis. Formerly Research Services Manager, MCL, and now Consultant to MCL in the area of Product Toxicology and Safety in the Use of the Company's products. TRAN 009685 HARTOLDMONOO11130 2 INTRODUCTION The wide 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 man. 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 wide 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 showed not only the peaks corresponding to the insecticides and their known metabolites, but additional peaks of unknown chlorine-containing substances. Towards the end of 1965 these unknown substances were identified by SUren Jensen, a research worker at the Institute for Analytical Chemistry, University of Stockholm, under the direction of Gunnar Widmark. Using 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 cause misgivings both to public authorities and to the general public. ......... Jensen and Widmark 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 conesl The conclusion reached was that the PCB's originated from burning industrial wastes and were washed down by the rain. Examination of feathers from museum specimens of sea birds suggested that contamination commenced in 1944. The original work of Jensen and Widmark has been extended and generally confirmed, notably by workers at the following establishments and much of the detail has been published TRAN 009686 HARTOLDMONOO11131 3 Great Britain 1. Laboratory of the Government Chemist, Cornwall House, London, S.E.l. (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, Sittingbourne, Kent. (Dr. J. Robinson and Mr. A. Richardson) 4. Monks Wood Experimental Station, (*Nature Conservancy) Abbots Rlpton, Huntingdonshire. (Dr. N.W. Moore) *EBtabllBhed 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 1963-4 there was a Government grant-in-aid of 701,000. Holland 5. University of Utrecht ...........................(Professor H. Van Genderen) _ U.S.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 Museum (M.N. Kirven) TRAN 009687 HARTOLDMONOO11132 4 This report is written following discussions with staff from Establishments 1, 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 Widmark. They are also visiting Bayer to ascertain its reactions as manufacturers of PCB's (Clophens). SUMMARY - 1. There can be no 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 will prove to be, but what evidence there is is reassuring. 3. There is little evidence to show how the PCB contamination arises. It may 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 slowly 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 this threat to our commercial operations. A. Visit to Freshwater Fisheries Laboratory, Pitlochry* Monday, April 2&th, 1969. ` : `- ' Mr. A.V. Holden - Officer in Charge. Dr. R.E. Keller - MC Dr. D.V.N. Hardy - MCL This visit was made not so much on account of contributions made to the subject but because Mr. 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 009688 HARTOLDMONOO11133 5 for the programmes of the O.E.C.D, countries concerned with the influence of biocides on natural environments, wild life, etc. He might 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 wejjks after which the concentration in the fish muscle was 1 in 10 . In other words there was a concentration factor of 1000 in 6 weeks: this would take place mainly by absorption in the gills. He 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'b 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 out for other bodies, e.g. the Nature Conservancy. Much of the work remains unpublished and he saw little chance of rectifying the situation. B. Visit to Tunstall Laboratories, Shell Research Ltd., Sitting bourne, Kent^ Tuesday, April 29th, 1969. Dr. J. Robinson - Biologist Mr. A. Richardson - Analyst Dr. Stevenson - In charge of Experimental Animal House. Mr.. De Corson - Laboratory Administrator. '...... ........ Dr. R.E. Keller - MC Dr. E.P. Wheeler - MC Dr. D.V.N. Hardy -r MCL Shell has naturally been concerned with the problem of insecticidal residues from the outset and the cost of the analytical effort and its interpretation must have been very considerable. To Shell the FCB 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 009689 HARTOLDMONOO11134 t6 toxicological interest might 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's but mitke a very sound approach to the insecticides problem and to its true perspective. Nevertheless they had collected some information on possible usage of Aroclors, for example, they had noted that the Coal Board disposes of 1,000,000 gals, of high pressure lubricant each year. Did this contain Aroclor? Ve thought it unlikely but questions concerning safety in use of Aroclors had certainly been referred to MCL by the Coal Board and it was therefore likely that Bone minor uses have been developed. There might conceivably be a Braall 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 muoh 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 100 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 Dieldrln. 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 PCB. Reference was also made to the work of Mr. Alabaster, Ministry of Agriculture, Fisheries and Food, on toxicological levels with fish. *4 .......It was agreed that many of the specimens submitted for analysis were not representative 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 PCB's can be found in the oils, they disappear during the hardening process so that margarine is free. TRAN 009690 HARTOLDMONOO11135 7 The decrease In bird populations which iB made much of by the Nature Conservancy and others cannot be attributed wholly to organic .chlorine compounds. .....Factors such as exceptionally...... cold winters (e.g. 1963-4) and the decrease in hedgerows (10,000 miles/year are eliminated in U.K.) must have an Important, effect. Reference was also made to wood preservation with PCP and to the possible effects of waste discharging, but this seems an unlikely source of PCB's. There was some discussion of the chick oedema factor which has been attributed to the use of trichlorethylene as extractant. Here Dr. Wheeler spoke of the highly toxic tetrachlorodiphenylenedioxide ' Cl /V ^Cl with which the Germans and MC have had experience. We outlined the main uses for Aroclors as being Dielectrics for condensers, transformers and switchgear. Industrial hydraulic fluids. Heat transfer fluids. Extreme pressure lubricants. Hot melt adhesives, Chlorinated rubber paints, and played down suggestions that they are used as media for insecticides and in Jet engine lubricants. No reference was made to N.C.R. Finally Shell made reference to some work to ascertain whether PCB's might arise through degradation of insecticides. The degradants were chemical agents and no success was obtained but it is still possible that some biological procesq might be able to bring about such transformations. We were given a brief opportunity to view the Animal Laboratory where much work was in progress on inhalation studies. Long term tests were in progress with benzene vapour on human volunteers, 8 hou-s a day with full monitoring of all appropriate factors. This is likely to become the standard reference for safety in factor operations. TRAN 009691 HARTOLDMONOO11136 8 C. Discussions with Representatives of the Government Laboratory at Monsanto House ' Thursday, May 1st, 1969. Mr. J.O'G. Tatton Mr. G.B. Collins Laboratory of the Government Chemist It It it if Dr. R.E. Keller Dr. E.P. Wheeler Dr. D.V.N. Hardy - MC - MC - MCL 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. As 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 extended and PCB's have been found in eggs, predatory birds, rarely in human food, and traces in cod liver oil. Human fat 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 cn air and on circumstantial evidence PCB must be present. 1 part DDT compounds/10^2 parts of air has been found. The analysis is 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 Association) has failed to find PCB in river waters at parts per 10^. Many samples are sent to the Government Laborat ry by the Nature Conservancy, but having carried out the analysis nothing more can be done as the source and significance of the sample are known only to the Nature Conservancy. ........... The peaks seen in the chromatogram represent only part of those observed in commercial samples of Aroclor 1254. Probably the middle components are- favoured by the analytical procedure: certainly peaks due to 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 009692 HARTOLDMONOO11137 9 and kingfishers. Dr. N.W. Moore (Monkswood Experimental Station) might be prepared to discuss their significance and the geographical factor. ...... Tatton considers that Jensen's............... peaks are more in line with Bayer's Clophen. He thinks that some of the bird samples are representative as they were taken from colonies. Tatton also referred to possible traces of PCB nature in occasional food samples, e.g. milk, mutton and beef fat. He will supply me with copies of 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 MCL work now starting on the biodegradation of Aroclors and suggested that our workers should contact him on the analytical techniques. He would be most happy to do so. D. Discussion with Representative^ of Cremer b Warner, Consultants, 140 Buckingham Palace Hoad, London, S.ff.l. Thursday, May 1st, 1969. Sir Frederick Warner Dr. David Train - Cremer fa Warner _ tt ff Dr. R.E. Keller Dr. E.P. Wheeler Dr. D.V.N. Hardy - MC' - MC - MCL This was a lunch discussion arranged to determine the possible value of this firm of consultants in the assessment of the PCB problem. Cremer & Warner have contracted 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. Cremer is Chairman of the Government Committee which has been advising on the problem due to hard detergents. Cremer & Warner are also advising on atmospheric pollution due to sulphur dioxide and smoke, and on the design and interpretation of data from the recording stations. They have also acted as consultants for the new potash project in relation to the effluent disposal problem. They have advised that the effluent should be discharged 1 mile from the shore at a minimum depth of 75 feet. TRAN 009693 HARTOLDMONOO11138 - 10 - They were interested broadly in our problem and fully appreciated that after all the analytical work had been done it would be necessary to interpret the data and to correlate........... it to safety standards in a way which would carry conviction with the authorities. They seemed confident that this area was one of their strong suits, but it is far too early to assess their ability to contribute to the present problem. D.V.N. HARDY JWB/HMH 6.5.69. Footnote (See p.4 - Summary, Item 3) Compare Jensen's findings that no contamination was observed prior to 1944. TRAN 009694 HARTOLDMONOO11139 Monsanto i D*f( turn irci (f[HtNCl TO i May 26, 1969 INCINERATION OP CHLORINATED WASTES RMK Memo U/lO/69 R. M. Kountz - RKOUN J c D. A. Olson. A. P. Pier - APIER _.W,... R. Richard - V/RICH Bob, in the Pydraul and ThermiTJoJ^-oi^a, we estimate that on an annual basisr-wo aouid~trSvethe following gallonage to incinerate: Pydraul - 50,000 gallons Therminol - 18,000 gallons These are only estimates derived from discussions with men in the Froduct Group. We have made no attempt to solicite opinion or Interest on the part of our customers. One source we have not polled, and that is Flndett. You may want to get from him the amount of material that he discards per year in relation to the amount that Jje-'l'eclaims on both Therminol and Pydraul. " /pke on/ I W IO fc I V ll HARTOLDMONOO11140 Monsanto S'. l*. Mmwrt iSItt OH)4*4-223# -0404NIC CMCMfCAU DIVISION John R. Fallon Product FwicfKMl ftwWi J> a __ _ Zfm.4.JL 7J~- /**> /w J\fL<JL&A------ <$Lr-^ JnlbrZ ^ /<& (A*-<ASV\ 4/1 aX*40^ C(^<yuJ<Le$ ?{(**+ iff% /jw/' ^ --t^J^Z+sA js'A ' A* .--"So ' : /{{jOeO ^ trrAir, -------- / ^ (pUGS? -- MA J'O QeG jtiis - JL4r& <<*^Uaj mH. bstxdlj fAt* -tZ-fe <wW, ........ cdt cv - fy'o&kK^ A 1 TNGS 0 1 6 1 0 5 HARTOLDMONOO11141 R. M- Kountz -- General offices April 10, 1969 incineration of Chlorinated wastes Mr. A. F. Pier Mr. W. A. Kuhn Dr. W- R. Richard cU^' ZU> 0. Some contacts are now being made for chlorinated waste incineration systems. This investigation is taking a three-pronged approach* 1. outside firms who might incinerate our wastes for a fee. , 2. incineration systems to which we could refer our customers. 3. An incineration system which we might install at either WHG or AnniBtcn. One of the obvious questions being raised repeatedly for all cases is either what size system do we need or what range of feedrates would we predict. Since we have dis cussed only material coming from our customers, we need your input. I don't see the practicality of setting up a system for G.E.'s 400 drums and then stopping. I would appreciate your giving some thought to thir^ at your earliest convenience and giving me some feedback, if we could get a handle on the anticipated amount per year or on any reasonable basis we can project a feedrate. I might add the reason this becomes significant is because of the HCl collection system. A very small system might use a water scrubbing system discharging to the sewer. Another method would be to circulate caustic and yet another larger system might collect the HCl for subsequent sales. Depending on the amount of BCl predicted, economic analysis will indicate the logical choice. Me will also consider using the present plant HCl collection systems. /ab R. Si. Kountz TNGS 016106 1 J HARTOLDMONOO11142 Monsanto TO : David Wood-et. Louia-B2SD May 29, 1975 PCB INCINERATION c. Paton ' J. R. Savage E. M. Potter-B2NK W. B. Papageorga R. C. 6prague-B2NQ `A. Leiay-1740 G. Johnson-1740 C. Field-B2NE T. L. Gossage W. Withers-B2SA R.'.ilAibiC-B 1HB'A' "* EXHIBIT NO A, We have all been concerned by the number of incineration shipments which have increasingly resulted int a) Need to clean-up trucks b) Need to specially dispose of solid wastes. Apart from cost involved and diversion of productive labor, Z understand your concern about the risk of increasing PCB in our own effluent due to the special handling involved. The causes of our problems are* 1. Customer use of old corroded drums. 2. Inadequate securing of bungs. 3. Overfilling of drums - allowing no room for ex pansion in-transit. 4. Customer does not always segregate solid/liquid waste. 5. Forklift damage to drums in loading at customers* 6. Insufficient inspection of load by carrier (not aware of hazard). 7. Drums not always labeled properly. 8. Drums not loaded securely. While all the above are familiar to us who deal with delivery of liquids in drums, we need to correct these deficiencies at our customers. I believe that the more irresponsible of our customers will not improve without some financial sanction. .................... I propose the following actiont A. Modify standard latter covering each ''rt-rn. 1. Clean up coats to customer account. 2. Segregation of solid waste and return to sender to customer acco-.-*- ' 3. Add instruction sheet for carrier. - I attach present letter (Attachment A) and proposed draft of standard letter (Attachment B) and carrier IRAN 074047 HARTOLDMONOO11143 -2- B. Latter giving details of new conditions for................ incineration (Attachment D). This letter should be taken by salesmen to responsible management level at each U.S./Canadian approved customer. It explains our current problem and the potential impact of the irresponsible on the total industry. Draft is attached. C. New label for returned drums (Attachment E) This incorporates latest warning statements and gives instructions in event of spill to contact 1) shipper; 2) Monsanto. D. Guide for customers shipping department. To improve understanding of procedure at operating level. Draft will be circulated week June 2nd. Cumming, I would appreciate your and Tom Gossage's approval to the proposed action. Would all copyees please comment by June 7 in order that we can proceed as quickly as possible? Thank you. . /deb Attachments David Wood TRAN 074048 HARTOLDMONOO11144 Attachment A fPresent) Monsanto - MONSANTO INDUSTRIAL CHEMICALS Cd~ BOO N, Llntffctrfh Kevttvartf t- Louia. MImouiI B3IBB Phni 014) BB4-I000 This will confirm our concerning incineration of your fluids. Enclosed are pre-addressed drum return labels marked "Disposal Only". The drum contents must be clearly indicated on each label. To prevent leakage, please use return drums which meet DOT 17E specifications (55 gallon drums, 10 gauge, 2 bung head; 5 gallon drums, 24 gauge minimum) . 'rne outside of the drums must be clew, free of fluid and not leaking. Cleanup or other cost affecting the carrier which are related to fluids leaking from drums will be charged to the shipper. Please show Monsanto Identification Number on the bill of lading and on each drum. The freight classification is Plastic Liquid NOI and the release value is 50$ per pound. Please ship all drums freight prepaid to: Monsanto Industrial Chemicals Co. Department 831 , Incinerator Sauget, Illinois 62201 Incineration charges are 5$ per pound, with an $8.00 per drum handling charge for each drum being returned. Please advise if you want us to invoice these charges against a specific purchase order number. Ml Ml USNIBHIN ^RMMRM Tran 074049 HARTOLDMONOO11145 Solids such as sawdust, ragB or sludge and aqueous fluids cannot be handled in our incinerator. For these materials we suggest you check local authorities and your own environmental department for an approved.... disposal method. Personnel in our Sauget, Illinois, plant have been instructed to refuse receipt of drums containing these materials and to return them to the sender at the sender's expense. Thank you for your cooperation. If.you have additional questions, please phone me (314) 694-3024, or contact me by letter at the above address. Sincerely, Enclosures C. R. Field Supervisor Customer Service Center TRAN 074050 HARTOLDMONOO11146 Attachment B (Suggested New Letter) New Form Letter for Incineration Returns This will confirm our............................................................................... concerning incineration of your ...................................................... fluids. Enclosed are _ pre-addressed drum return labels marked "Disposal Only." The drum contents must be marked clearly on each label. To prevent leakage, please use return drums which meet DOT 17E specifications (55 gallon drums, IB gauge, 2 bung head; 5 gallon drums, 24 gauge minimum). The outside of the drums must be clean, free of fluid and not leaking. Drums should be free from corrosion and bungs tightly sealed. As a condition of return for incineration, clean-up or other costs relating to fluids leaking from drums will be charged to the shipper. Please show Monsanto identification Number on the bill of lading and on each drum. The freight classification is Plastic Liquid NOI and the release value is 50 per lb. Please ship all drums freight prepaid to: Monsanto Industrial Chemicals Company Department 831, Incinerator Sauget, Illinois 62201 Incineration charges are currently 50/lb. with an $8.00 per drum handling charge for each drum returned. Please advise us if you want us to invoice these charges against a specific purchase order number. Please note that solids, such as sawdust, rags or sludge cannot be handled in our incinerator. Additionally, liquids containing more than IX water can cause damage to the refractory lining of our incinerator and as such, cannot be accepted. For these materials, we suggest you check local authorities and your own environmental department for an approved disposal method. We also refer you to ANSI CIOT Guidelines for handling and disposal of capacitor and transformer ankarch containing chlorinated biphenyls. This is available from American National Standards Institute, 1430 Broadway, New York, New York 10018....., ...... - - ......: '' ''' ' .......... It is a condition of shipment to us for incineration that any drums containing solid materials will not be accepted and will be re turned to the sender at the sender's expense. Additionally, if we, in our judgement, need to separate and repack un.cccptable solids or liquids for safe return to sender, a handling charge of $100 will be billed to sender. TRAN "074051 HARTOLDMONOO11147 -2- We recommend that the attached instruction should be attached to the carrier's copy of the bill of lading, and be brought specifically to the attention of the driver. We thank you for your cooperation in arranging the appropriate handling of this consignment for incineration. Please call us again to set up any new incineration arrangements which may be needed. We need to send you instructions for each return to ensure that you are familiar with any changes in our procedures. If you have additional questions, please phone me (314)694-3024 or contact me by letter at the above address. Sincerely, /deb C. R. Field TRAN 074052 HARTOLDMONOO11148 ATTENTION> DRIVER Attachment C This Shipment contains POLYCHLORINATED BIPHENYL (PCBs) which some studies have shown may be persistent, an environmental.................... contaminant...and possibly injurious to certain forms of bird, aquatic and animal life. Prevent any entry into the environment through spills, leakage, vaporization or otherwise. Spills and leakage must be collected. DO NOT STORE with food, animal feedstuffs or pharmaceuticals. Keep containers TIGHTLY closed. In case of leak or spill, contact: 1. Shipper 2. Monsanto Company - call collect (616)271-5835. IMPORTANT! DO NOT LOAD any drums which are leaking or not tightly sealed. LOAD securely to prevent drum damage in transit. TRAN 074053 i ma HARTOLDMONOO11149 Attachment__ D All Approved U.5./Canadian Dielectric Customers Dear sirst ___________ ____ ___ ____ He with to bring to your attention problems associated with disposal' of waBte chlorinated biphenyl products in our incinerator at Sauget,, Illinois. 1. Many recent returns have been in completely unsuitable drums which have been severely corroded and unsealed. Some drums have been overfilled so that expansion in-transit has not been contained. Loose stowage in trucks has resulted in movement of the load in-transit. The results have been spillage into the truck and in some cases contamination of other goods in the truck, which then had to be destroyed. We have had to hold trucks at our plant for cleaning, attracting demurrage charges and diverting plant , personnel from productive tasks. The potential cost of clean-up had such leaks in-transit caused detectable environmental contamination would be significant. The truck cleaning at Sauget increases the risk of escape of PCB-containing effluent from our own plant which could jeopar dize our ability to continue normal controlled production. Such irresponsibility on the part of a few can have results which could effect the continued availability of PCBs to the whole capacitor and transformer industry. We seek your assistance in ensuring that returns from your company are appropriately packed, sealed and stowed for return. As from June 1, 1975, costs incurred in handling inadequately packed returns will be billed to the company involved. 2. We have requested prior contact before EACH return so that we can send the required number of PCB Warning labels. We are.............. still receiving drums without warning labels. In the event of * spill in-transit, the absence of warning labels could be a factor in assessing liability. We aeek your help in ensuring that we can send you enough suitable labels for each return. TRAN 074054 HARTOLDMONOO11150 -2- 3. We attach copy of the form letter that we will ibe sending with labels to advise on correct return procedure. You will note that this letter advises that our incinerator cannot handle solid waste. It is designed to handle liquid streams only. We still receive drums containing rags, saw dust, and metal and wooden components. In the past, our plant personnel have taken care to separate solid wastes and have arranged separate special disposal of the solid waste?. This will not continue. As from June 1, 1975, a charge of $100 will be made if labor is diverted to separating solid waste. Additionally, the solid waste will be suitably packaged and returned freight collect to the sender. While we wish to .continue to assist the electrical industry in disposal of liquid waste chlorinated biphenyl in our incinerator, we cannot and will not permit the service to become inoperable because of abuse by a small number of companies. We thank you for your assistance in regulating returns from your company. /deb David Wood TRAN 074055 HARTOLDMONOO11151 o w* o c 9 CO 2 . cz m 2 w P>C ma O cmo O> s|2 oa :/5 ni r Zm O CO -1 m S rO T> Tf S3 o o c 5; 31 m CrnO CmD O 2 < TM 2 22 m o S s Q) D fy* 8 ? Q. - CO 3 (0 Irt (T| O rc>M C a eg CL ci n 2m 2' "2 .; d 30 si O -< *2~ 2 <3 (*_DA .Lf2*.rr-*i 1 o> 3 < I< 0) trt co 5 2.E g; s w = 01 3 ^-a na2--nn> 3 CD P 33 3O CO 3 rn ni> c _ o-1 5* 3 cr x i-2 m (O 33 5 2 m m PC < it o' 3. -g-8 3 3 | ffi.s T) 3 2 o' r- O 33 M 5 5D1 X) A ij> Vi 71 O- W O o> O 3. 2- |9L oa |2. t3D 3=b "3 ~n o X) H z r> z n 70 ^2/ > inn] T :--a rn (C i^"n 2 r~ <3 a [ml (S> or? 0 M HARTOLDMONOO11152 David Wood-8t. Louis-B2SD February 24, 1978 ^ )5 WOOiKWTIO*.......... ............. D. L. Sllney C. V>tOB SU <9. Potter *Ui dnsTSHi Tftfi mt*. . 1* Z attach a copy of tba latter w sand to outoaan Inquiring about incineration of Kf fluid*. 2. Also, attached la a copy of the label for return pcodrt vast* and an advlae note that we requeet be given to the carrier. 9. Ooepanlea wht. regularly nalce returns receive a veil chart to place in their shipping area to focus attention on good handling practice. Z attach a reduced copy of the well chart and a copy of the text. 4. we do have problems with return in bad draw from tine to ths, and J. C. Weber is developing a pro cedure to handle these caees. David Wood HARTOLDMONOO11153 Monsanto I (MO** ihiMl A COCA* ,0-- David Wood-St. Louis-B2SC DAI t JCCT TO July IB, 1974 DIELECTRICS SEMINAR SEPTEMBER, 1974 MEETING 17TH JULY PROGRAM COMMITTEE P. G. Benignus T. L. Gossage ' W. B. Papageorge *I It became clear during our discussibn 'that the program should follow a sequence: . 1) Definition of Environmental Problems Surrounding PCBs; 2) Indepth Review of the Defense of PCB Continued Use; 3) Conclusion that Use of PCB Can Be Continued. Wc wish the program to allow customer participation and to reflect a balance between capacitor and transformer manufacturers, and large and small manufacturers. Ideally, there should also be some contribution from the limited number of overseas manufacturers who may attend. On the above basis, the following program evolved: 1) Status report on environmental issues concerning FC3 around the world. No guest speakers would be involved in this section since we wish to concisely define the problem before the seminar without getting into over much discussions of different corporate viewpoints. U.S.A. and Canada would be presented by Bill Papageorge, the European situation by Al Vodden, and other world areas by David Wood. 2) Effect of PCBs in the Environment. We believe that this heading should cover biodegradation, isomer differentiation, and test procedures to satisfy the capacitor industry pro blems, and secondly, migration of PCBs in soil to reflect the rather different situation of transformer manufacturers. We suggest that this is handled by Scott Tucker and Al Vodden without guest speakers. ' TRAN 028069 IN . IO RtV. I'll EXHIBIT NO.j2L HARTOLDMONOO11154 -2- 3) Methods of testing PCB in effluent streams. This topic should be divided into four sections: A) Presentation by Ed Stewart on clean-up of our own PCB facility; ... B) CED Department - Monsanto ideas..for controlling.... PCB at customer locations; C) Capacitor industry comments, preferably by Mr. Hydrick of Sangamo; E} Transformer customer comment by Mr. Shepherd of Westinghouse. 4) Disposal of waste Aroclor. We suggest that this be handled by a panel comprising Jim Savage, Bill Papageorge, and Earl Potter, and should aim to cover incineration, transportation, cleaning and disposal of drums, damage to bulk containers in transit. We anticipate that at the end of Item 4 would form a breakpoint for lunch. - 5) New Fluids. Under -t;his heading, we would cover work o" Aroclor 1^16, Aroclor 1043, and non-PCBs with emphasis being low on non-PCBs; however,as we hope the EPA standards support the continued use of PCBs. We propose that this section be handled by R. Munch and J. G. Bryant. 6) Transformer Fluids. We seek a presentation by G. E. Rome, Jim Kinney covering the search for alter native fire resistant transformer dielectrics to be followed by a presentation by Bill Richard in dicating that Monsanto has not neglected transformer fluids in its Research program, but that new major developments have not yet evolved. We shall seek in this presentation to ventilate the Monsanto pro duction problem if there is a general move from higher chlorinated isomers and explore the concept of a transformer fluid based on Aroclor 1248. Items 2 through 6 are designed to indicate the number of areas in which a defense of continued PCB use can be mounted. TRAN 028070 HARTOLDMONOO11155 -3- 7) Economic influence of askarel use on U. s. economy. Here we seek a presentation by Ed Raab of General Electric of the economic data.. presented- in Washington. We hope to set a positive note with this presentation to support continued use of PCBs. 8) Consumer attitudes. Under this heading, we would seek positive presentations on askarel transformers and askarel capacitors. Oux first choice for transformers is Niagara with Ferranti Packard as reserve. Our first choice on capacitors is Jard with Mallory as reserve. It was suggested that after each section, we should allow a 15-minute period for questions from the floor and that as a last stage, the committee should consider whether there were any specific organizations and ques tions we wished to introduce into the program. Would you please let me know if the above fairly re flects the conclusions of the meeting and whether you have any further additional comments to make before we seek final approval of this format. ' /deb David Wood TRAN 028071 HARTOLDMONOO11156 9. "Wood (92SO) Bovbr 7, 1974 V * H. . *rgen - I28L W. C. Moor* - 1010 W. B. Bapageorg* Z told him that w* had requests for nch a study and that v* w*r* currently reviewing what resources Monsanto could apply to such a program and what type of sampling might be required. He accepted that we night be in a position in December to be more positive. D. Wood Ai V. , >, **- -/l- &W EXHIBIT NO.,3# * PLAINTIFF'S EXHIBIT /AC 1*+ i> i.iJ 300 2612 HARTOLDMONOO11157 HARTOLDMONOO11158