Document 5DLvRn534Gzzp9KkxVN6GOQRz

4Monsa* nto *0tf iuocaTI*m> JJlJJC *u October 25, L972 vinci imofiKe i TO ' Mr. W. R. Corey - B2SL Mr. W. B. Papageorge - B2NA Mr. H. S. Bergen - B2SL Mr. E. P, Wheeler - A2SA Mr. J. F. Stapleton - B2SA __________ Sjtr. K. W. Easley - 1920 Mr. P. J. A. Marsh - 5040 The attached two articles on PCB appeared in Ambio, a publication of the Royal Swedish Academy o Sciences, dated August, 1972. Authors are: Sopeq Jensen - "The..PCB Story", and Gensyu Unseda Poisoning in Japan." stw Attachments MOMS 207B07 I V.. 4 t m ' fr" .** *'H.3 rpi^C^Pr* "^'- * w^v ^ < -0-i F VS?''.*?. . -* 'r *vr`TM jj***- rZjt&i*:. ../-tT_-"*" -.V. Jm' jfe ** ***ri jT - *>"? *rv;%- !*- r a-- - * -V ` o- - Ti*r Jvi * ^1 C*.. ' *Vr: i r* * H.:^- y v~ ,"-r,?-'Trv-.v'?S-: . vV-'-ay--,* - _ r* J ^ ^ rv ;* : VA.^.J?< '- m* " '* *** '^'l" **' vt$ ! -.-. . -jj, '- .'- S'-j- r- T t'a.r-J,,-i T - -- . -i- - ul) > * , - - * ..' '. _* l^- 4K^^f_"ar - *- . ,, * _ , , _# * -^- "J ~ -' *r 1 * 'in*-'-.;.-..' - - *a>7 -' k ;'ll --J.' ,--... r :c; '-,v.* * ** , -* 1<> -1,VrViVcw**v#y.: fcl/ 4 ,, * ^ . ^rv 7 /. r**jr // ' ' ^ H itiLli *<i-J HONS 207808 'MBYSOREN JENSEN 'A . . ' . The accumulation of PCB in nature and thus in the food chains was unknown to scientists until 1966, although the substance had been used industrially since 1929. , It war the Swedish chemist Spren Jensen who, when analyzing DDT accumulations in nature, accidentally found enormous quantities of unknown substances that were later on identified as PCB compounds. PCB constitutes perhaps the most stable group of organic substances in existence. Itposes, therefore, a severe threat to life-forms. In Sweden this discovery has ted to a taw prohibiting the use, import, manu facture and sale of PCB without permission from die authorities. In this article Sdren Jensen gives, for the first time, the complete story of his discovery of the substances. He also presents test results which show the PCB levels in blood samples from PCB<ontaminated Japanese and other persons. The article can be read as a detective story with a moral. It can also be considered as an example of the kind of unpleasant discoveries we can expect unless environmental controls are applied to all dangerous substances before they are used extensively, before they can contaminate the Earth. PCB pollution in nature war discovered at a rather late date, but considering the circumstances. it is perhaps surprising that was discovered at alL While the contamination of nature by PCB was sot de tected until 1966, tbe accumulation of DDT is nature was first recognized in the 1950's. During the late 1950's and early 1960's biologists and chemists became increasingly aware of DDT and mercury pollution. Tbe presence of these two substances in the food chains was discovered before the presence of other contaminants such as PCB was revealed, largely because of the obvious connection in time aad space between the use of DDT and mercury and the negative effects eaused by them. When farmers used mercury-treated seed, pheasants that lived io the fields and ate tbe seed died. When DDT was sprayed on plants to kill noxious insects, the birds K\ing on the insects disappeared (1). In these cases, where there was rather dear evidence of cause-and-effect in situations that were relatively easy to observe, biologists could turn to analytical chemists for final proof of their h>potheses (2) HONS 207809 This was not and is not possible with a substance such as PCB that is blended for internal industrial use and enters nature through the "back door", Le. with the emission of industrial smoke and sewage lvater. An important aspect of tL-s story is the development, in the late 1950'a, of apparatus sensitive enough to detect a thousand milliooth of a milligram of a substance This amount is sufficient for analytical purposes if a standard is available, but is not enough for a structure determination of an unknown substance. Thus it was not until this daw that the science of analytical chemistry possessed the tools necessary for the analysis and discovery of DDT. DDT was first synthesised by the German O. ZeidUr in 1174 and was first introduced as an insecticide shortly after World War IL But even if DDT bad been pot into use immediately after its invention, its contamination of nature probably would not have been recognized apy earlier. And at a consequence, them would have been an 80-year accu mulation of DDT to deal with instead of a 15-year-old one. . In 1964, the department of analytical chemistry at the University of Stockholm, where I was employed at the time, was required by the Royal Swedish Commission on Natural Resources of 1964 to estimate the level* of chlorinated pesticides, especially DDT and its metabolites, that were present in human fat tissues. Shortly thereafter the project was expanded to include wild life samples. Figure 1. Ga cfcremutogrum from purifUd trad from wtill4*Upd tag!*. All psukp but DOT and DOE war* unknown. Cahimn: #F M 4 % an Gao Ctirom P (KMOS-Vaitod). Ovan Wmparatura ta. tM*C. Ntougaa llow 30 ntJ/minute. MYSTERIOUS SUBSTANCE DISCOVERED The work started in October 1964. The analytical method used at the beginning was taken from available literature, but was later on modified slightly (see Experimental). As DDT is fat soluble, dried homogenates of muscle samples were considered to be suitable for the experiments. Ether extracts from the samples were cleaned up by means of thin layer chromatography on microscope slides. The final fat-free extract! wen injected on a gas chromatograph fitted with an electron capture detector. However, it is well known that with this system positive identification is not possible because several different compounds may have the same retention time on a single column. The risk of making a wrong identification is minimized by the use of double Column systems, but it is never fully avoided. Al though the detector is very sensitive to chlorinated hydro carbons, it is by no means sensitive exclusively to such compounds. Thus many substances containing oxygen or phosphorous have shown quite good responses. When the analyses were carried out along the lines set forth above, the work often resulted in chromatograms as shown in Fig. 1. Only p.p'-DDE and p,p'-DDT could be identified by means of their retention times. Among these two there were numerous peaks whose retention times did not agree with any of the known chlorinated pesticides. They were totally unknown to us. When a different gas chromatographic column wns used the peak that had been assumed to be DDT was sometimes shown to be an un known one. COLLABORATION WITH ECOLOGISTS Often up to 14 peaks could be found in t chromatogram of extracts from a pike aod as they were not described in the literature the possibility of a pure analytical solution of the problem was at that point impossible. To get a final solution it was accessory to collaborate with ecologists The first hypothesis to consider was that the unknowr substances might belong to the common natural products Therefore the Swedish Museum of Natural History in Slock holm collected pikes for analyses from SkLne in the south to unpolluted Lnppland in the north. But the farther nortf U4 AMIIO. VOL. t HO HONS- 207610 the origin of the samples, the lower were the levels of the unknown substances; thus it was clear that those substances did not occur naturally in pike. The mercury problem in Sweden had just been recog nized, and some organic mercury compounds were shown to possess a high response on the electron capture detector, so the museum collected pheasants, one of the species suf fering most from the mercurials. However, it was shown that thess birds did not contain the unknown substances. - Could they possibly be unknown metabolites of the chlorin ated pesticides? To check this hypothesis, 'one feather of each white-tailed eagle specimen ires obtained bom the museum's collection from 1888 up to present and the feathers were analyzed. The unknown substances were pres ent already in 1942, but chlorinated pesticides were not used until 1945, consequently the unknown substances could not be metabolites of these pesticides. Fig. 2' shows a series representing different levels of a food chain, including young salmon, pike end white-tailed eagle. Both DDE and the unknown substances increased up through the chain. At the same time there was a shift of the relative intensity of the unknown substances towards the late numbers in the chromatogram. But this was not especially pronounced, indicating that all these compounds must be very stable. It should also be noted that the aquatic ecological system was quite different bom the terrestrial system represented by the elk. There was a possibility that these unknown compounds could be metabolites of other pesticides such as the phos phorous insecticides and the chlorine-containing herbicides. However, neither treatment with alcoholic potassium hy droxide, nor concentrated sulphuric acid changed the chrom atogram, except that the DDT and DDD were dehydrohaiogenated by the alkali treatment and the epoxy pesticides disappeared during the sulphuric acid treatment These treatments indicated that the unknown substances did not contain anything but hydrogen, cartooa end halogen*. I wutCTCM PCB IDENTIFIED Fortunately for this investigation a white-tailed eagle was found dead in the archipelago of Stockholm end could be examined. It contained enormous amounts of the un known substances. Thus the extract bom 1 g of the muscle bid to be diluted up to 5 1 if a 10 pi injection on the gas chromatograph should be within the Linearity range of the electron capture detector. 20 mg of the fat was run on the microslide thin-layer plate as mentioned in the experimental part, and the eluate from the plate was evap- 20 mm Figure 2. Ca* chromatogram*: residua analysis of body Fat fro-r different ecological level*. Column: QF 1 + $F 96 mixture. fruCCIiOrj AMIIO, AUGUST |tn MOWS 207811 125 Anted to 50 pL This solution wu then injected into the combined (u ehromntograph-mus spectrometer. Figs 3i and 3b the chromatogram and one of tbe miss spectra. The mass numbers equal to the molecular weights of the unknown peaks could be read to 324, 338, 392 and 426. Astonishingly enough, tbe molecular differences were constantly 34 mass units. Thu constant difference for the lint time showed that there was a relationship in the origin of the unknown substances. Tbe presence of chlorine could easily bo recognized from the unusual isotopic pattern 75 per cent is "Cl and 25 per cent Is *TQ, which gives two molecular peaks two mass units' 'apart with the relative intensity of 75:25. With two chlorines per molecule the intensities will be 57 per cent (two **C1), 37 per cent (one mq and one "Cl) and 6 per cent (two *TQ) respectively. For x chlorine per molecule there will be peaks for M + 2 x (x -- 0.1.2.3................where M is the molecular weight calculated by chlorine~aa **CI). By meins of this isotopic pattern the following relation* ships for the unknown peaks, wen postulated: Molecular weight: 324 358 392 426 Chlorine per molecule: 5678 i 40 min i-------------------------- 1 m min An explanation for the relationship between the unknown compounds can be read from the following equation (RH is a hydrocarbon): RH + Ch ------- RO + HQ M_________ 2 35__________ M + 34 36 Figure* 3* end 3b. Cti chromatogram (r combined moor opactromobry.gaachrom* graph? of whlto-talltd oogio extract. Mel etar weight* for A, . C, D and E>. 383. 3 910, 934 end 331 (taturotod hydroearbor Fi 319 (DOE). C. K t, L and M: 334. 3 903 end 43a (chlorinated biphenyl* with I* 7, 7 and ( chlorine etema). The molecular weight of the parent hydrocarbon (PHC) could thus be calculated: M(Pko "M--x Mft+i Mb< where M is the molecular weight of the compound having x chlorines per molecule and for M=426 and X" 8 chlorines: MffxowdZd-aao+a-isd (of course all the unknown substances will give the same value for PHC). The most plausible formula for a hydrocarbon with a molecular weight of 154 is C,jHWl which is only satisfied if the parent hydrocarbon is biphenyl, and logically the unknown substances were polychlorinated biphenyls, which have been given the name PCB. The identity was later fully verified by injection of Clophen A SO (a synthetic chlorinated biphenyl mixture) on the mass spectrometer. Furthermore, extensive gas chromato- graphic investigations proved that synthetic PCB gave pea with retention times identical to those of tbe unknown pea. from the white-tailed eagle and the other species inves gated. It took about two years to answer the question of t mysterious peaks of the unknown substances in ihe chrom togram. Thus PCB was finally identified in 1966 (3). In the past we have learned that extremely persiste substances are potential contaminants of tbe envirowne and that the risk that they might accumulate via food chat increases if the substances are also fat soluble, such as DC and PCB, or if they can react with the proteins in the org nisms, such as heavy metals and organic mercurials Aval able medium in an objective investigation of environment pollutants might be digested sludge from sewage treaune plants, which contains both lipophilic substances and pr 126 AMBIO. VOL I MO MOMS' 207812 t<n tad can thus enrich certain types of contaminants in domestic and industrial wastes. As digested sludge has been exposed to microbiological art. ck, only the most stable substances can survive to be environmental pollutants. Compounds may even be converted to stable metabolites with higher toxicity than the p-unary contaminants, as is the with the microbiological methylation of mercury. This system should prove valuable in the objective search for unknown pollutants. If sludge had been analyzed earlier, --PCB might have been discovered as the result of a system atic search inf1***1 of by accident. . After the identification of PCB was finally made, it be came apparent that many DDT analyses made in the past might be wrong because of PCB interference and it seemed probable that the risk for DDT contamination of nature had been overestimated. Instead, analyse* had indicated contamination by PCB. This is true for analyses done by iimm of the methyl silicoDc.and Apiezone columns often used up to 1965. In these old columns p.p'-DDT, especially, has been shown to overlap with PCB 10 (ths last major peak). Thus the DDT apparently, present in the chromato gram from the white-tailed eagle shown in Fig. 1 is actually PCB 10. This can be seen by means of the QF 1 column that is now often used (4). WORLD-WIDE PCB RESEARCH Since the discovery of PCB accumulation in nature was published in 1966. the presence of PCB has been reported in organisms from all over the world, and the subject has been reviewed by many authors: Risebrough el nf. in 1968 (5), Risebrough in 1969 (6), Veith el of. in 1970 (7), Gustaf son in 1970 (6), Peak*)! el of. in 1970 (9), and Reynolds in 1971 (10). Many attempts have been made to saalyze PCB in the presence of the chlorinated pesticides, but do really satisfactory method has yet been described. The same is true with the problem of the quantification of PCB. As PCB Is produced by direct chlorination of the aromatic hydro carbon biphenyl, numerous bomologues and isomers are found. 210 different substances are theoretically possible, and If the chlorine Is distributed as evenly as possible on the two phenyl rings, 104 are still possible. Recently Sisson and Welti (11) have, in an excellent work, identified 69 dif ferent compounds in a PCB product used in industry by means of mass spectrometry (MS) and nuclear magnetic res onance spectrometry (NMR). In a normal column used in residue analysis, no more than 20 peaks are seen, and it is obvious that severe! peaks come from the overlapping of different compounds. Nevertheless, the mistakes made are small in relation to the igntffrinry gf ^e biological ex periments. CONTAMINANTS Vos el aL (12, 13), found that not ill commercial poly chlorinated biphenyl preparations had the same toxicity; * Significantly higher mortality, liver necrosis and chick oedema-like lesions ware found in two out of three prepa rations tested. They found an active factor in a polar fraction and they concluded that the structures were tetri and pent* chlorodibenzofunna. These compounds might have been formed from a phenolic contaminant in the PCB in the same way as 2J.7.8-tetrachloro-dibenzo-p-diojun (to which they are related) is fanned from 2.4.5-trichkrrophenaL STABILITY PCB is an extremely stable mixture against both chemical and biological attack. Thus it can be boiled with potassium hydroxide in ethanol or fuming sulphuric acid without de gradation. It is reported that PCB is dechlorinated by means of ultrtVolet light (14). PCB is said to be highly non-in flammable if the chlorine content is above 4, but many authors have reported that it it easily degraded at elevated temperatures. Thus Karlsson and Rosin (15) found that around 950*C PCB will be destroyed within a few seconds. Ordinary oil burners, however, obviously are not equipped to do this, or else it would be difficult to explain the pres ence of PCB in the air, especially around big cities. Recently it has been shown that PCB wastes in oil can be destroyed in existing industrial facilities through the burning of oil at 1.400*C with a deficiency of oxygen. This process is used in a cyclic system for the manufacture of ammonia as well as for other purposes. With this method factories can use waste oil containing PCB in their production pro cesses, and can, moreover, function as destruction sites for PCB by mixing additional PCB with this oil. The waxy layer, on the needles of pines around Stock holm often contains.PCB. This cau be explained by as suming that when waste oils (which often contain around 50 ppm of PCB) are burnt, the PCB (at least to some extent) passes through the chimney, and into the environ ment. Another source of PCB might be the burning of solid wastes. The discharge of used PCB into the sewage treat ment plants is indicated by the presence of PCB in digested sludge from these plants. That the biological stability of PCB is high in relation to DDT is seen in digestion experi ments. When DDT and PCB are added to activated sludge amcio. auoujt >n RONS 207813 127 and digested anaerobically, DDT will be metabolized-- mainly to DDD but alto to store polar iubstances within a lew days, while PCB remains intact alter a 40-day period. It is this stability of PCB that stakes it useful in industry. In 1929 the electrical industry introduced PCB in capaci tors and high voltage transformers because of Its good tnnlring characteristics and because PCB is non-inflamm able. PCB it now used in e number of different palms to make them resistant to chemicals and oxidation. - USE OF PCB IN SWEDEN PCB Is not produced in Sweden^but the enmtal import of bulk material amounted in 1969 to 600--700 toss, about 12 times the import of DDT. This situation was probably representative for many industrialized countries. Most of it was used as non-inflammable oils in capacitors tod trans formers. PVC and chlorinated rubber paint contained 5-- S per cent of PCB to increase the stability against chemicals and oiidatjoa. Beside this, there Is e 3--5 per cent addition to paints used on boats below the waterline. SO--85 per cent of all small boats and SO--60 per cent of the larger ships in Sweden have used such paints. Gradually, it his been discovered that PCB occurs in e number of products in which there was no reason, earlier, to suspect its presence. Recently we found that large quanti ties of PCB were present In certain carbonless reproducing paper sold on the Swedish market (am NCR). This paper was used in forms which are prevalent hi banka, libraries, etc. The PCB content was about 12 g per kg paper, which means that an original plus two copies in A-6-fonaat (10.5 cm X14 .5 cm) contained about 110 mg PCB. PCB is no longer present in sacb paper. The stability of the substance that makes it so attrec- TsWs I, Annual PCS eee In Satlaa Maitrial Unit tist Total amount of PCB Capacitors Transformers PVC and other paints Boat paint Insulation paste 20 and 2--4 kg 1 ,, 500--2,000 kg 1450--500 tons 1,000 tons 400 tons 160 tons 55 tons 15 tons 35 tons 555--605 tons tire fo: industrial use is the same property that causes the accumulation of the substance in ecosystems and the food chains. BIOLOGICAL EFFECTS - The rcute toxicity of PCB is not very high. There is a relationship between toxicity and chlorine content which healed to different maximum allowable concentrations with a higher number of chlorine atoms, the maximum allowablr ha air is 1 mg/m* air, and for the kinds of PCB that have a lower chlorine eooteet St is 0.5 mg/m*. No maximum allowable level for PCB contamination in food has beer established yet A typical symptom of PCB poisoning is fatty degener atm of the liver. One case of mass death of salmon fry it a Swedish hatchery showed this typical picture and the PCI source could be traced to anti-fouling paint used in th< hatchery. . Effects on workers handling PCB have been reports and include various damage to the skin, apart from the live degeneration mentioned above. It is estimated that th avenge Swede hat a concentration of PCB of around 3--< mg per kg body weight Damage to chicken embryos and inhibition of hatchin, occurs when 0.0*1 ml of PCB is injected into eggs. Thes experiments have not been followed up to test the lowes level at which these effects occur. PCB (and DDT) are now known to activate the meta bohe enzymes of the liver. The consequence of this is a increased breakdown of certain reproductive hormone: which could result in changes of the reproductive rate i animals and man. PCB aocidenJts have been reported from the USA anc Japan. In Japan (16), leakage from a corroded pipe containing PCB that was being used as a heat-transfer or resulted in the contamination of the rice oil with up to 2 > of PCB per kg. Thousands of people who ate the cor taminated rice suffered from chloracne-like skin eruption Just before people fell sick, one million chickens sufferc from chick edema-like symptoms and about 700,000 diet The chicken food originated from the same factory. Several thousands of persons are said to have suffert from PCB poisoning in Japan, although only 1,000 patien were officially reported to have been suffering from tl disease, which is called "Yusho". Symptoms are skin cru turn, pigmentation, visual disturbances, abdominal pain ax fatigue. Only a few patients recovered, since no treat:: 128 AMOtO. VOt- l NO MONS 207614 Flfim 4. Cii chrenategrame *1 bumaa Wat. al PCI. DOT, ODE. ^-BHC mnd HCB(T). 1. b|HMH (PCB paVant) ' t JMwa (niiMl) ' 3. Amaricu (Hv*4 4 )raar la Ja^an, tfitit 4 yam bi Sweden)' 4. Swede .. methods have been discovered. Ia some euti death oc cured. Pregnant women patients an reported to have borne babiea with highly pigmented skin. Several babies were born dead, la tome cates apparently unaffected women had babies with pigmented skin. Such births occur even today. PCB IN BLOOD SAMPLES . Recently, 1 compared the PCB level in the blood of two Japanese suffering from PCB intoxication (contacted via contaminated rice oil in 1968) with that of some Japanese and Swedes who were not known to ba especially exposed. The sampling was dose in 1972 and the results are shown hi Table 2 and lug. 4. As expected, the PCB-intoxicated Japanese have more PCB in their blood than the other persons investigated (29 ppb hi mean, compared with 10 ppb). Because of the small number of samples in this analysis, it is not possible to determine--on the basts of these results alone--whether or not the high level of residue in the patients is due to their high PCB intake four years ago. But the striking difference in the blood levels of -BHC between persons living in Japan and in Sweden can be taken to be a rather dear indication that a persistent chemical actually ean remain in the body for at least four years. The substance jf-BHC is isomeric to the Insecticide , lindane and often occurs as a contaminant in lindane prepa rations. In all blood samples from Sweden, the levels were close to the detection limit of 0.5 ppb. In blood samples from the Japanese, however, the levels ranged from 6 3 ppb to 200 ppb. Sample No 4 is from a Swede who has lived in Japan during the last two years; the fS-BHC level is almost as high as in the Japanese samples. Far more interesting, however, is sample No. 11, taken from an American who lived in Japan from 1964 to 1968. Tim person has been living in Sweden since 1968, but the 4-BHC is, nevertheless, at the Japanese level -This tleariy HONS 207815 Table 2. f-HC, DDT, DDK end PCS to human bleed. Analysis accardtof ta tha feraUa eeM/heaane Mtlwd. 'V> x ' 1 Swede e Stockholm 2 3 Swede 9. Stofictotm * Stockholm 4 Swede t Stockholm >1970, Tokyo >72 3 JepeetN 9 Stockholm 194*--70, Tokyo -72 c Jspeime 9 Tokyo 7 Jipeime 9 Tokyo 1 JipiMM t Seotbtra Jtpee 9 JipUMI 1 Southern lapse (petieal) 10 Tiptutft Southern lapse (petieal) 11 Amerkaa t Ispsa 1944--4* ,, Sweden IMS--72 m$?$ fresh wci|h( basis l-BHC DDE DDT PC Cl4 U 04 4.7 7.1 (A U 20 21 41 9A 4J <2 10 7.2 M 11 34 19 9A 24 1J 1.4 1.4 4J ` 3.1 1.1 4.1 11 7.0 34 4.0 9 (4 ti 4 4 3 1 22 33 t4 demonstrates that a persistent chemical can actually remain In the body for four years. It follow] that this may also be true for PCB. ` Another conclusion that can be drawn from this investi gation is that the levels of PCB and DDT in the analyzed samples are of the same magnitude, but that the chlorinated Insecticide lindane used in Japan contains mom 0-BHC than that used in Sweden. * _ It cen be seen from Fig. 1 that the relative amounts of the different PCB compounds do not differ in the sample! from the two countries. It has recently been found that low-chlorinated types of PCB can be metabolized at a rather high rate in mam malian organisms. This means that the PCB residue tends to be more similar to high-chlorinated types of PCB (regardless of the chlorination degree of the formulation Ingested) because the small amounts of tha high-chlorinated homologues also present am unaffected, and thus wfB eventually dominate. This may why such relatively small amounts of PCB (less than 100 ppm) am found in tha bodies of dead Japanese who had been afflicted with PCB intoxication. As tha PCB which contaminated the rice oil is said to be of tha 30 per cant chlorine type, it may be that all the low- chlorinated types of PCB wem metabolized before death occurred, leaving only small amounts of the high-chlorinsted ones. If this is true, the PCB levels at the time of intake might have been from ten to 10Q jimes higher than the postmortem analyses indicated. PCB BANNED BY LAW Investigations initiated by the National Swedish Environ ment Protection Board concerning PCB disposal showed that between 10 and 15 tons of the substance were stored at a firm awaiting safe destruction methods. Some C. carried 100--200 kg portions of PCB to solid waste pi; and one firm dumped the wastes (around 100--200 into the sea. It wu only recently that a method of desu mg PCB was discovered, as mentioned above. In January 1972 a Swedish law went into effect proh. log the use, import, manufacturing and sale of PCB will the permission of the authorities. PCB probably occurs in more substances than tf which are named and forbidden by the new law. An exao of this is mentioned above. But the National Swedish viroament Protection Board, the authority responsible seeing that the law is observed, can in such cases de that the law shall also cover certain specific products, possibility of applying the law in this manner is prese being investigated by the Board, THE MORAL OF THE STORY Hie accumulation of PCB in nature was discovered a dentally, as was mercury contamination. What conclusi can be drawn from these findings? Similar discoveries of the accumulation of other eberm are quite likely to occur at any time. This should sen emphasize the need for close cooperation between ecotoi chemists and other scientists. It is necessary that responsible authorities invest in r power and equipment to facilitate an unbiassed scare! pollutants at an early stage by systematic analysis. These are the measures that should be taken if the i aging and perhaps irremedial effects of a substance a. be discovered before and not after it has entered th< vironmenL This appbes especially to substances that . mu late and are highly persistent, as we have learnt fror history of PCB. 130 AMS 10, VOU 1 HONS 207816 EXPERIMENTAL AX mlnuts uatd wan ndbtUhd. U addition, huaa* ou abo p*MU< kk cmaunM lulphur* idd and dinillM tram Min biwlda Mathybaa (Aland* mi dulm with a 5 par ml aaludoa of pniatolw eerboeni*. washed with water aad dried *hh calcton L 1C. iof*. NcmUiiti tnm tot 111 Ner*e Ytttrbm Cotuns fta Swi dhh) in Helsinki 193ft, p. B4. 1 T. Wtuetraark e*d ft. SiOsuuad, M / rippHel Andie !**!#* , f, 1 L ft. Tuan, Nr* fdanri* 32. p. til (1964). -` * L tt 0. Wldtoarit, OCCD frdimitmry Study (19*1, primu Sampftnp and Eahvclto*: All sampiiapi van cocduaed at (be Mhw at Manual History to Start bnbn, Tsnplas war* Hand at --#>*C all analysis. Baton utnoio*. ifta aanplaa wen haaopniaad to(titer with .a doable aaouat at aohydrotu aodian talphaia by PMaoa at aa tonrtibli liuaniaaliai **-- wish htuoe v*s caniad oat to a ViaMat apparatus. A/ttf taw bom the MinK.vas enpamtad, beitop tba fal to a mbB. weiphed Mss tuba Coed to tba bottom'of a paardonaad Hart. PartStd akroma mi blaana dowa to lb* tuba balora wriphtop. Mdhybpo diloride *u add'd to a ndfksaot anaaal to that lb* final aotottoa aoatatoad 20 ap fat par 100 at aotottoa. Tbto layer ehconetopiapbyt Tba steepel O mad ami watted vtt maihaaol (IXal to X|X driad abb rnianoa and ftoafty actlaaMd at 140*C erami(be Mtcroieope.sljdn (15 x 76 no) van aaramd vtt a tony at 34 dbopi aMtil vaiar >0 Ibat tba lajar mi 0J H ihkfc. Tba plataa van stored anardnaiad to a desiccator abon coaotttiatad sulphuric add aad actinwd at 140*C pdor to an. fir (Maaa at a Hamilton arriapa 10M at (ha atom aaratlaaad fat aatadoa to nnhrtaaa chlorid* was-strippnd oato aach pitta aad tba plataa van danlopad widl awthykaa cfclond*. Attar air dryiep, tba fat boat could ba r*coraised tratos a hap aa a bow* ahadov up to a balfhi of about too cm. With a naor Mada tba Aapl iton iba fat front mi scraped dova la aa lotto* tuba ria a (uaari. Tba tub* ooaatxad at a (kaa tuba (10 cm X 0J cm LdJ oat# vbicb vaa naked a capillary with aa toaar dammar at OJJ m (outar diantir 0J aa). Tbrouph lb* capillary vaa draw a teflo* Mb* vtt aa outar ilaoMtar at 0.11 me vindb vaa nada coaiml by ****** at a vam aoattl plait rod. Tba ddortoatad hrdrocarboai van vaahad out tram lb* ulieaaal wii* atom at m hum diathyl atbar (2:1; v/) uadi *a* nl bad paaad through. J. X. Pisabrouph. P. ftekd**. D. B. PakaS, J. a. Hervtaa aad M. K Kimn. Mono* 720, p. 10H (1*44). 1 1L Ktottroupd to Gtomtoaf PaOour, O. G. Bet aod M. W. Millar Bds. (G C. Tbomaa. SprtototoM, BL. USA. |t). 7. O. D. Vatt aod G. P. Laa, IParar Jtaaaasrt 4, p. li} (1970). .GO. Gamattoa*. tadnamnad Sdener and roWai 4, p. II* OMfi . 9. D. K Paakaft aad J. L. Ltocar, MtSdnct 20. p. 931 (1970). 10. L. M. Xqaolfa fladdat Xrdm (Laapa and Spnapn Vcrlap, Barfto) J4, p. 27 (1971). 1L D. fttsaoot aad D. I. W*M, tmamt f Ctoannatrutoiy 60. pp. 15-- (1971). 12. J. O. Vos aad I. H. riitos, Fetontopy oodetpptfrd PbanMcatopy 17, p. 454 (1*70). 11. J. O. Vo*. J, H. Rauaato H. L. vaa dar Maas, M. C tan Hoanr da lnuv aad B. M. da Voa, Pood and Cawimca roaculopy t, p. 42] " 0770). 14. S. Safa aad a Htoatoptr. JVonra 232. p. 441 (1971% 13- L. Karlisoa aad E. ftosta, CAntoca Script* I. p. 41 (1971). 14. Xaportr #/ tor study */ "rantou", Study Group af Youtoo, Faculty af Madid**, JCyusho Uaireruty, Fukuoka, Japaa (1949). 17. Tba rather ih*ak* Pmfetaor G. Widourit, Head e( th* Drpanmaat af Aaalytical Ctomtstry at th* University ef Stodth dm for veluable help vtt th* PCfaideutifkalio*. Ga* elwvnafagrephyt Aa PCX (up la towtaaa pnfa) aad tba ttlortoatad pardddai an aatnaadr dUlfcak to Mpanta vtt aar aninivm pal danlopad, at kart Ihn* difiaraat Systran vara and for tba t*pam> tiout, aaontr oaa 4 par mat IF H nmhyl sMceoa, oa* * par east QP 1 floor (Qieoo* aad a third toad* bp toacbaulmMr niaiai tba tvo naotianid to tha propaittoaa tv* to aj(to laapaathaly (to th* foHowing mOtd tba X)-column). p.p'-DDB, a^pC-DOO aad ditidna* could aot ba aapamiad atlFM column **r aauU gfODD aad o.p'-DDT. On tba pun QP I columa k vaa potafaia to fully aepamta PCB p*k 10 (lb* last major pack) from p.p'-DDT, but a* tba othar haod p.p'-DOD aould aot ba aapantad from tba PCB paak f (lb* tost aujor peak but oaa). Th* XJ colama pan a full aapaiattoa at GDI, ODD aad DDT tor both Iba oitltoptn aad pan-pin isototn. Tba a&plam aotuam (ISO cm, U. 0.11 cm) vaa iHaaiaad aad died vilh th* aolid support (HMDS-tnated I0&--120-matt GraChroa P) oonrad vilh (ha abonJiaaltoaad stationary phaaaa. Th* m-- warn placed to th* pat chromatograph (Variaa 104) with aa electron capture dattetor (tritium). Th* datactor aad th* atjaeior wen bald at 200*C and th* cohunn otca temper*tun was choaaa to gin p.p'-DDT a letaatioa tioi* of 30 ounuta* whaa th* solnnt niration rim* w*a 14 tec. (*<*! to a mean pas apasd of 13 cm/ate.), Maaa apactoomoby; Th* uon columns as abon van abo pbaad to a LKB 0000 combined pa* chromatograph nui apactromatar. Sftrta fenaott, Ph. D, h* ha*it haad of the Nation*! Svadiah Enwenment Protection Bo*rd'a Special Analytical Laberaiory alnca It* aiUblfahmant to I9P9. AMOtO. AUGUST tm HONS 207817 131 PUS Poisoning m Japan by Gentyu Umd The most serious PCB catastrophe the world has a known took place about four years ago in Japan, where thousands of persons are said to have dis- played symptoms characteristic of PCB intoxica tion. Gensyu Umeda describes the dLease here. In March of 1968 a (rest many cases of a strange, previ ously unknown disease appeared in the northern and western parts of the Japanese island of Kyushu, particularly in the Fukuoka and Nagasaki prefectures. Clinical and chemical analyses were performed and in August it was determined that the disease was brought on by some kinds of organic chlorides. ~ In November it was discovered that the specific cause of the disease was a contaminant in Kanemi Rice Oil, a common food-stuff. The oil was manufactured by the Kanemi Rice Oil Co. Ltd. The contaminant was identified as Kanechlor 400, which is the brand name for a particular PCB (polychlorinated biphenyls). The disease was named "Kanemi Yusho", There are an estimated 15,000 victims of the disease. However, only 1,081 persons have been officially diagnosed as victims of Kanemi Yusho. Local governments and the central government refuse to officially recognize many of the victims who should, in all fairness, be supported fi nancially by these government bodies. CLINICAL ANALYSES - Clinical analyses of Kanemi Yusho victims revealed that there are four types of the disease. Latent type The patient has no significant physical symptoms and no subjective symptoms of Yusho. Nontheless, PCB has been detected in patients of this category. For example, when analysis was performed on materials removed surgically, PCB was found. And when women with no obvious symp toms gave birth to babies who displayed typical symptoms of the disease, it became obvious that those women were contaminated. Another example: babies fed with mother's milk displayed pathological symptoms in six months or later. A baby newly bom of a contaminated mother of the latent type displays some characteristic physical symptoms such as hypersecretion of chccse-Iike or mucoid discharge from the eyes; disturbance in growth; ard pigmentan of the skin and nails and of the mueous a tmbrane of 1 eye and mouth. :' Vleceral Type ' The patient of this type has no characteristic dermatologi signs. Instead there are complaints of complicated syn toms as wed as physical signs of pathological processes the viscera. Examples of these are general fatigue, nau. or vomiting, mild jaundice indicating liver injury, cohc-l attacks of abdominal pain, diarrhea, productive cou chronic bronchitis or bronchiectasis, asthmatic attacks, z pneumonia. The occurrence of pathological changes of t kind has been demonstrated by x-ray analysts. In cases of the visceral type, PCB is detected in spurn blood or material surgically removed, and in many stances there is an increase in the concentration of trig cerides and preheialipoproteins in the blood. Latent and visceral types are seldom officially recogni; as victims of PCB contamination and are seldom diagaoas Yusho. But these cases are of great significance w regard to the disruption of the environment by PCB a the contamination of the human body by PCB which . liable to occur in the near future. Manlfeat type Many of the cases generally known by the term "Yush belong to this type. The characteristic physical signs a subjective symptoms include chloracne, comedo-like eri tions and follicular accentuation as seen in the photo the opposite page and the photo on page 134 Oth symptoms are dark-brownish pigmentation of skin and ne and of the mucous membrane of the eye and mouth; hyp secretion of cheese-like discharge from the eyes; loss hair; loss of libido; general fatigue; numbness of the tremities or n?uralgia-like pain; headache; stomachac abdominal pain; nausea; vomiting; dizziness; disturban of higher nervous activities (e.g. forgetfulness), local i pairment of blood circulation; vomiting as n result changes in conditioned reflexes to disturbance from fc Photo* on oppoailt pag* and on page 133 chloracnt, com* hke eruption* and follicular accentuation. Sea cofour photos m ln*ido hack covar of japan*** palitnts with tom# of tilt aymptom* of the manif**t type of Kanimi Yuaho. HONS 207818 AM IK). AUGUST 1*12 HONS 207819 foods; Battening or deformation of nails; deformities of joints and bona; poor development of teeth in children; morphological changes of teeth of * pathological nature. In addition, other pathologically complicated changes have been observed recently. Although patients suffering from these symptoms are typical Knoemi Yusho cases, many of them have not yet been officially recognized as victims of the disease. Tardive Type Some earn of a delayed (tardive) type have been observed. Physical signs and symptoms specific to Yusho are mani fested, regardless of the amount of PCB the patient ingested. The symptoms appear one to three years later. The reason for this is not dor at this time (1). TREATMENT AND PROGNOSIS Yusho Is very dirfhmir to treat and Its prognosis is not always benign. Treatments administered in attempts to ameliorate the suffering and complicated symptoms of tha patients are generally not successful.. ..with one exception. Patients are slightly ameliorated when human placenta that have been kept in cold storage are administered by injection or transplant. These measures are especially effective with regard to the nonspecific symptom complex or the nonspecific reactions of the organism as a whole. Acupuncture and moxibustion (used in the Kamp6 medical approach, a Chinese method of treatment) is re cognized to be more effective in dealing with pain such as headache, stomachache, stiff shoulders, low back pai and pain or numbness of the extremities (2). Concerning tbe prognosis, the following symptoms a in my opinion the most serious ones: 1. Functional disturbance of tbe higher parts of tbe cents nervous system particularly of the cerebral cortex. Th is especially serious in young children, who may dtsplr symptoms at birth or during the first years of life. 2. Changes in tbe cardiovascular system are being observe* This is an important tendency at tbe present time. Th changes may relate both to the function of the heart, a demonstrated by EKG analysis, and to the peripheral cir eolation. The occurrence of signs of local impairment c blood circulation was already mentioned. 3. A new tendency that has recently been discovered tbe deformity of bona; especially deformities of the finger toes, ankles, wrists or vertebrae. The deformities are a* cooptnied by'pain. 4. In some cases changes have been observed in the teetl e g. breakdown, loss or sudden snapping of teeth (3). Reference* end Neteei t. C. Uraeda, inert 67, pp. 6--1 0977). 3 C, Urania, Min irtn irro M, pp. 17--JJ (1970) 1. O. Umeda, Chnlnt Asptttt el PCt feuemnt (Abstract ot the )i Coiptn ot the Japanese Auocutioa of Induutul Health, To.i April, 1971). Geniyv Umeda. M. D. I* heed ot th* Department of Clinical PatMtsfy at the Kltak)rvi)r Roiotrch Institute for Environ* jental PeOutlea In Japan ns RONS 207620 i i > w t5*v '>-. -. .7_ **'Ll * w- * *- U,''"V^Vi ''^*-'" * W --' > .*** -*< ,*' ' , Vs. x* .'! '"1.S ' * IV r,"y -.*.*/ V' * "**) iriCM HONS 207021