Document 6ROgo8jEg0v8eNeZXJd5V152d

7 Pr^I Detailed Examination of Polychlorinated Dibenzofurans in PCB Preparation* and Kanemi Yusho oil M. Morita1, J. Nakagawa', K. Akiyama' S. Mlmura1, and N. Isono3 'Tokyo Metropolitan Reaeerch Laboratory of Public Health, 3-24-1 Hyokunln-cho, Shinjuku-kv Tokyo. 100 Japan *Tokyo Metropolitan Unlvoralty, Megro-ku, Tokyo,Japan Polychlorinated dibenzofurans (PCDFs) are known to be highly toxic substances. (HOFMANN 1958) Through chick embryo_bioassays, Vos at al. (1970) identified two kind of PCDFs as toxic components in PCBs. Subsequent investigations have revealed that several PQDFs are present in a nuober of PCB preparations. (BONES et al. 1973* ROAOI and POMERANTZ 1974, NAGAYAMA et al. 1976) However, only limited informations are available cm the isomer components of this toxic material. PCDFs were recently reported to be present in Yusho oil which gave rise to a large scale of human intoxication. (NAGAYAMA et al. 1976) "Yusho", namely oil disease, is a peculiar skin didease characterized by clinical manifestations as follicular accentuation, acneform eruption, pigmentation of the skin and nail and hypersecretion of Meibonian gland. The cause has been considered to be PCB poisoning (Kuratsune et al. 1972) but it was recently suggested that the toxic role of PCDFs was not negligible in the causation of Yusho. Hence, detailed characterization of PCDF components seemed to be necessary in Yusho oil. The present paper will describe detailed analytical result of PCDF exponents as to the r.unbers and compositions in Yusho oil and sixteen PCB preparations. M----a--t-e--r-i-a--l-s----a--n-d----M--e--t-h--o-d-- Samples Yusho oil was the product of 12th Feb. 1968. PCB samples examined were Kanechlor KC300, KC400, KCS00, KC600, --Aroclor T64, T241, T1242, T1248, T1254, T1260, Clophen A30, A40, ASO, Phenoclor DP4, DPS, DP6. AllPCB samples were not specified in lot lumber. Used PCB samplewas Aroclor T1248 used as a heat transfer agent in chemical factory during two years. Operation condition was not specified. Analysis PCB sample(lg) was dissolved in 2 ml of n-hexane and chromatographed over Florisil column. The size of the colunti was 1 cm in diameter and 30 cm in length. 20 grams of Florisil (80/ 100) preactivated at the teoperature of 630aC for four hours, was packed. After the first absorption, 200 ml of n-hexane was passed the colum in order to remove most of the PCBs and then SO ml of hexane acetone mixture (95:5) was passed. PCDFs were recovered fTom the colum by eluting with 100 ml of acetone. The recovery was more than 90 The acetone fraction was condensed ___ f ; ! ; |i j (j u 1 j ' ! ; il1' )> j: I ! t ; ! |, 11 1| ! ; * | n| '4. IN, fc, I a |*rr t.1 67 4 T.l. <4tr. S'* Ytk Inr. HONS 003347 to the voline of 500 jil with Kundera-Danish condenser and nitrogen gas flashing. An aliquot of the condensed solution mbs injected to gaschromatography-mass spectrometer (Shimadzu-LKB 9000). The following condition was employed. Colunti Dexil 31 on Chromosorb WAW DCMS(100/120) 3my2m Carrier gas He 30ml/min. Ion. Vol. 70eV Temperatures. Colism 270#C Injection 300*C Separator 300C Ion source 310#C Mass spectra were taken at every five second with a computer system (MS-PAC). 192 spectra were obtained from 2 to L8 minutes after injection and the selected mass numbers were plotted on section papers for qualitative and quantitative analysis. Quantification was made on the assumption that each PCDF specimen was ionized to the same extent by the electron of 70eV regardless to the difference of the degree or the positions of chlorine substitution. Amounts of PCDFs were calculated by conparing their peak areas with those of known anoint of the standard sanple. Result and Discussion Mass fragmentgrams of chlorinated dibenzofurans in commercial PCBs and In Yusho oil are shown in Fig. 1 along with our standard sanple. Standard sanple was synthesized throu^t chlorination of dibenzofuran by chlorine gas under the presence of ferric chloride and iodine. Average chlorine number was 4.7. Standard NC JOO i Fig.l. Mass fragmentgrams of PCDFs in PCBs and Yusho oil monitered by parent peaks( 270, 304, 338, 372). MOMS 003346 T 241 Eighteen PCDF isoners (three trichloro-, five tetrachloro-, five pentachloro- and five hexachlorodibenzofurans) were dmonstrable in these staples. Peak 6 was tentatively assigned to 2,3,7,8-tetrachlorodibenzofuran fron the coincidence of the retention tins with the authentic sanple. Other isoeiers were not identified in their chlorine positions. It is worthy to ' : MQNS 003349 note that almost all PCBs have similar PCDF isomers. FCDF concentrations are listed in Table 1. In regard to the occurence of PCDF in PCB preparations, the following four mechanism may be probable. Reaction (1) means that dibenzofuran contained as an impurity in technical grade biphenyl is chlorinated to PCDFs in the process of PCB synthesis. Gaschromatographic pattern of our standard sample, however, is fairly different from that of PCDFs in PCB preparations. Therefore, mechanism (1) may not he the major route of PCDFs. Vos et al (1970) suggested the mechenisa 2) as a possible route. However, gaschromatographic pattern of PCDFs produced by heating PCB(Aroclor 1248) with sodiua hydroxide were different from that of PCDFs in PCB preparations. Thus, the mechanism (2) may also not a major route for the formation of PCDFs. On the other hand, mechanisms (3) and (4) seeai more probable because used PCB has a profound PCDFs with similar isomerism. When PCBs (Aroclor 1248) were sealed with air in glass tube and heated at 300C for two weeks, increased amount of PCDFs were found. Produced PCDFs had a similar gaschromatographic pattern as shown in Fig.l. At the same time, the formation of hydrogen chloride and polychlorinated biphenylols was observed. This reaction was catalysed by transition metals or their salts. Detailed investigation is now in progress concerning to this reaction. PCDFs were concentrated in Yusho oil. The ratio PCDF/PCB reaches to about 1.11 which may be five hundred times higher than that originally contained in KC 400. Nagayama et al. and Mlyata et al (private coneunication) recently identified PCDFs independently in Yusho oil and reported the PCDF/PCB ratio as 0.5t and 1.2% respectively. Both results are comparable to our result. PCBs which had been originally used for the heat transfer agent was KC 400, however, the gaschromatographic pattern of PCBs in Yusho oil was rather resembled to that of KC S00. This indicates that lower chlorinated biphenyls were removed by evaporation in the deodouration process of vacuum distillation to result the concentration of PCDFs which are less volatile than PCBs. Furtheremore severe temperature conditions enployed in the company might give rise to the profotnd formation of PCDFs. Metals presented in the heat trnsfer tubing (stainless steel) might catalysed the reaction. Yusho disease is a chronic intoxication caused by the consult ion of rice bran oil (Yusho oil) contaminated by heat transfer oil (KC400). Yusho patients are considered to have ingested about 2 grans of PCBs in average. Assiming that the MQNS 003350 Table 1 PCDF concentrations in Yusho oil and PCB samples (pp) Yusho DP4 DPS Oil DP6 KC300 KC400 KC500 KC600 1 2 0.02 3 - 0.1 - 0.2 - 0.1 - 0.1 0.2 4 0.15 0.7 2.0 0.7 2.6 3.4 0.7 0.1 5 0.09 0.3 0.3 0.4 1.8 6.9 0.3 - 6 0.28 0.7 2.2 0.9 2.2 1.6 0. 7 0.1 7 - - 0.1 0.1 0.1 0.2 - - - - - - - 0.1 - - 9 0.03 _ _ _ 0.3 _ 0.1 10 0.53 0.9 1.4 1.5 0.6 4.5 0.1 0.2 ii 0.33 0.3 0.5 0.5 0.4 3.9 0.3 0.1 12 0.42 0.4 0.8 0.6 0.6 0.9 0.7 0.1 13 0.02 - - - 0.8__ ' - 14 _ ' 0.2 0.1 0.3 _ 0.2 0.5 0.2 15 0,12 0.3 2.5 5.1 - 0.1 0.5 14 0.64 - - 0.1 - 0.4 1 4 0.2 17 0.04 - - 0.1 - 0.2 0.2 - 18 0.01 - " - - - 0.5 - Trl- Q. 02 Tatra-- 0.52 Iint<<- 1.33 Hexa- 0.81 Total 2.68 _ _ 0.2 _ 0.3 0.2 _ 1.7 4.6 2.1 6.7 12.2 1.7 0.2 1.6 2.7 2.6 1.6 10.4 1.1 0.5 0.5 2.6 5.6 - 0.9 3.1 0.4 3.8 9.9 10.5 8.3 23.8 6.1 1.1 * Used PCB Peaks 1-3,4-8,9-13 and 14-18 correspond to trichloro-, tstrschloro-, pentachloro- and hexachlorodibentofurans, respectively. ratio PCDF/PCB Is one percent, the total Intake of PCDFs reaches to Z&ag for average patients. Although there is no way of blowing the toxicity of PCDFs in association with the various %ywptcma of the Yusho disease, there is a possibility that PCDFs were potentially contributed to the Yusho disease. ' It is also noteworthy that a crude rice bran oil of the seen origin as the Yusho oil had given rise to a large scale of chick death several months before the outbreak of huaan intoxication. More than five huidred thousand chicks were died in similar syiqitoaa of chick edema disease through the intake of food prescribed with the crude rice bran oil. (KCHANAMA et al. 19(9) Chick edema disaase is knom to be caused by several Continued (ppm) T64 T241 T1242 T1248 T1246 T1254 T1260 A30 A40 A50 - _ - _ _ _ _ 0.3 0.1 - - - - 0.2 - - 0.6 0.3 0.2 "- - 0.1 - - 0.7 1.1 0.3 1.7 1.1 0.3 0.2 1.9 0.2 0. 7 0.5 3.0 0.3 0.2 1.8 0.1 1.1 0.1 0.6 0.4 2.7 1.7 2.4 1.1 0.2 0.2 2.7 - _ 1.0 2.1 3.6 0.3 0.1 - - - 0.1 - - 0.2 0.1 - 0.2 _ 0.2 0.1 _ 0.2 _ 0.2 6.3 1.5 1.0 0.7 1.8 1.3 0.5 0.3 3.1 2.2 0.8 0.6 1.0 0.6 2.3 0.7 0.2 0.1 2.2 1.0 2.3 0.4 0.1 0.8 1.4 1.6 0.1 0.1 0.7 0.6 - - 0.1 - * " 0.1 0.1 0.9 0.1 0.5 0.2 _ _ _ 0.3 0.1 _ 0.7 - - - - 0.2 0.5 0.4 - - 0.3 1.5 0.6 : 0.5 0.7 0.3 - 0.8 _ 0.1 _ _ _ 0.3 _ _ 1.6 1.5 0.7 4.8 2.4 2.3 0.5 5.8 0.1 0.8 2.3 5.4 8.3 9.4 2.7 2.2 2.3 5.6 3.6 0.9 1.0 6.9 4.1 2.0 0.8 - - 0.7 1.9 0.5 - - 1.8 16.2 5.9 4.5 2.8 12.4 5.6 2.2 4.9 13.8 14.9 chlorinated dibenzodioxines. (CAKFRELL 1967) Wefailed to find a detectable aaiount of chlorinated dibenzodioxines in the rice bran oil. Polychlorinated dibenzofurans might have played a serious role to the large scale chick death in Japan. There is no evidence that FCDFs are present in ecosystems. It is reported that octachlorodibenzofuran is less rapidly absorbed from food than PCBs. (Zikto and Choi 1973) Di- and Triand tetrachlorodibenzcfuran were not detectable in juvenile atlantic salmon fed with PQ)F containing food. While, some isomers of PCDFs were noticed to be very persistent in the body of mouse to which PCDFs were administered intraperitoneally. Detailed investigation seems to be necessary to elucidate the 72 HONS 003352 distribution and tha biological liquet in the environment of these highly tonic substances if we consider that at least several ppma of PCDFs were discharged to the environment conconittently with PCBs. References BOWES.G.W., SMONEIT.B.R., BURLINGAME,A.L., deLAFPE.B.W. and RISERROUCH.R.W. : Environ.Health Perspect. No.5,191 (1973) B0IS,G.W., MULVIHILL.M.J. DeCaiq>,M.R. and KENDE.A.S. :J. Agr. hod Own. 23, 1223 (197S) CANIREU.J.Sr : Chem. Engin. News 45(5), 10 (1967) H0B**,H.Th.: Arch.Exp. Path. Pharisk. 232,228 (1958) XGHANANA.M., SHOTA,S., OGURA.Y., MORIWAKlTM. and KAWASAKI ,M. : Nat. Inst. Aniai. Hith Quart. 9, 213 (1969) KURATSUNE, M. TO3UMJRA,., MATSUZAKA.J. and YAMAGUCHI,A.: Environ. Health Perspect. No. 5, 87 (1973) NMAYAMA.J., KURATSUNE,M. and MASUM.Y. : Bull. Environ. Contain. Toxicol. 15, 9 (1976) RCMOi,J.AT7>. and PCMERANTZ,I.H. :Bull. Environ. Contam. Toxicol. 12,330 (1974) VOS.J.G., NOBIAN.J.H., VAN DER MAAS.H.L., TEN NOEVER DE BRAUW.M.C. and DE V&S.R.H.: Food Cesmet. Toxicol. 8, 625 (1970) i 1 73 ? HONS 003333 CHLORODIBENZOFURANS IN PCBs AROCLOR 1254 ANNISTON NEWPORT (1974) KRUMMRICH AK - 38 1974-75 RANGE -- RHESUS FEEDING STUDY (Kl-02-602) YUSHO OIL KANECHL0R-400 BASIS CONCENTRATION (PPM) 2-3 4-6 --- 6-7 5-33 10-12 5 5,000 HONS 003354 ixs'v AJ fi^rp4TbA~ C Hov) ^ .... . * .6 UK-if 11?V- 75 ^U**-`t Jf.at^i... ^OZiQt CK/^O^-toT.) 0 a*JUbM-ri - 9 fl~0 Jb%a~to laa0 TL^vwJw-/- <^rfw^ti2^ /O - 3- 7 7 -v C s i-r^rdjj ^v ^..irfZfc^rv P 2- 3 L4-C -? s- 33 \o - rz Sy dTTti 90 HONS 003355 'Q<BP /i;.irre ; FROM cr ;v;... i p;t isohi1- *ni fetk-1 f But- r Seist Federal Rtiearcn Station CH b&iQ HatflSail. Switzerland | 4nd Cnrittoffer ftappe Oepartnt af organ. Cneaistry, University >f 5 - 'O' Joel. Sweden Introduceipn Ihe oal/cn l^r ina'i -i J i: en;o f ur ?r. < PCCFs , ilrut Cure see De i : ar* a se-" 'S .- r :i ./( he aronatic ti,onas, ir .cental, b > o 109 c u J anc t j>-- ... re, yinilai CO in.- poiycn lor lU'.t] i'e*nzc-p-dioins (PCUJs. tee Win* 91 Cl. * Cl, hONS 0 0 3 3 5 6 7** PcOft ***e been identified urdesired trace contaminants in cMropn?r>ois, IMir derivatives lu 9**ne>y acid and i* polychlorinated biphenyls {PCBs; * Host recently, PCflfs h*. been ir fly as* end Mm gases of Municipal incmcretor* and industrial netting facilities.*' 13 T*/ Might to ubiqeitous products of cotoustion processes 11'** PCBs are industrial che^i-ais aid; use and they are no* u.awi r, oe widely distributed ift the to'irowm. -it-.ougn tne then**! conversion of PCBs into PCS#* under j/olytic conditions could oe esec'.td. >Mrinui evidence to our knowledge r*JS'*.eJ prior to Our pre-,',Cu r : n.u PCBs Cl, XCT CL PCDFs ro tr, increases levels ; 4 a* in tr presence of I gened-s o*f use 1.I5 ape-range) *r 32>rvo ii. a pee netted to JOQ1 for n a PCS used i neat ezenange system for '.tended i" Our prfirous pjoars rjv toorted on the forrdtion of PCOfs from tne pyrolysis Jf ci*rcul r'6 ,>' .In : I.- iO, 15 .'ictc yyrpl.yses were carried Out in Staled quart; aim -arjouit i 'r "* -ssence of air at te-ioeretures of SOO-fQO C. The h = Ics of tne PCDfs -r n :'s r.inie. In addition to PCDFi, .nreacted PCBs, .rli'inaiod bertenes. r.apn: i :'i> i'-: o*nr cnlormatid ceapjurfls ere also observed, '/ i found as possible inttraoi*ie jroduett. 5: jrs :$, ,,e n4*f furinpr shown that SCSI of the rajor - -i i ,:fK ;nc i^'e at those fomed in tne pyrol,sis i '.is. jumj stroi.j s,,p, ir: tnai t-se rCOfs originate ; uCa"trOI tej Purr; J 3' util , .nui.ij.4l PCL ISuJnrrs, ae ha.u fOu'3 Mit ` -illj.irg three . : c,. .rol,t* 4'e ir: raU-uul > ira ..t na dvsur cea ' -i.i 'fiCin; '0 o-fri:ent P^Cf toners fra* tn* i,r* 0" Cl, Cl Cl Cly Cli^O'^Ci, reaction route 2: ;IOtJ of > 1 >noi>ng a 2.3-cnlonne shift) :i, ci ci h i reaction regie 3: (lots of uitno-wCl) Cl, Cl H Cl) ci, ci, ciy In tmt paper now the occurrence of tnese reaction routes i tne pyrolysis of moiyiduai PCBs is further documented. Tne foraMtion at PCOFs was mst);a[*c m pyrolysis ezpenaents using 3 teir*-, 5 pen:*-, 1 he.4-. 2 hepta- and 1 octacnkrooipneeyl. Our e.perieents snow the generality of the above reactions, ar.c t: ese var. oe used :o predict tn* fomatior of specific ?Cufs. A fourth. additional reaction route *s found to occur with soae PCS isooers: [ loss of ortho-ti3 HONS 0033S7 fol/Cnlorihatrd ngr.cr/ls useo far pjrol.s-, fifteen PCS isomers were csuinec .artnut sour.es isaoer. uerr if^ukec for isacaru uuri*., : stnte or >w JtstriCuU siiyla u*' S wer* wbtiined arc ..ru, .as fuura I of \ * Ptes onia.red duiectabte ..ant - 5 . -,J, ; C C 5ur-,j *IOrOt.yrulySI> ol PCS* JiiU.I P\* ijfrs | lou .n ca.n . ' -U- 1*> '. if ul,s 'S caiu.- to g^cl/ted ir t in -. ....-L as .............. . . . - u!. .' .. *1 -,s . 1 : fable l. tiii-iLJ2iiSSl-S_22_li'22-l2SSiiSiiS2 iaapoond *aufx; 2.3. >. 5-tetrac.il lerodtphenyl 2.3,j,62.6.2 ,6' 2.3.1,6,6-pentatHorofc i.reny) 2. .j.2' ,5`2..6.3' ,4`- 2,4.6.2\4'l.J.i.V ,5 2,6,6,2* ,4* .S'-ncaacnlorebipAenyl 2,4,6.2 ,4' ,6` 2,4,6.2',4`.6'2,3,4,2' ,1* ,4'2.3.S.2'.3'.5'2,3.6.2' ,3' .6'3.*.S.3' ,4- .S' 2.3.4.5,2`,3`.4'-iiepucnloroPip*enyl 2.3,4.S.2',\S - 2.3.4,5,2' ,3' ,' .5' -oclacnloropipneny) ; )r. j. HcKinnev. iiatianal I' <estarcn Triangle Pan, ,C . : ?f CnI ltiroonental waltti Sciences, b Or, K, Andertson, G>ii /arsi .*et. Jwl, Sweden C ?f* Corp., Hope. *!. ii$A. ;; ,ii/ of Or J. McKinney d * >. C.A. Uacfinseis'.sr. unr.s Pt/ sf j'scibolo. Stocknpln, Sweden e > 3r. 1 Hatuda, Oiucni 2s- * Primeceuticel Sciences, furuoka, Japan t uC-HS Analysis 1 rir.Bi^an 1003 ;aoruuJ e G 36 -n ID 0(-1 / gla.s tj; ! ' t< ia i platinum .apil'.ar, ir.-r -- desc-'Oed. 10 naeer, tr.e coi.u ,S4"? -ritr of eljt>3ft( tn" 4 less sieei Cube. in a first pnote. caepiete second pnase. we sar.les were specific ucu-u'on cess Irjg.-* 2/0, 334, 338. 322. 136 and i-. mstruiApt aitn t! sou.-ce and coupled Co a v3 b ;l. n s u^ca. ir; ^U.sn was interfaced to tr.e MS Tne userating conditions were as previously ;-:.d sonewnat niijner elution temperatures for PCDfs colore. interfaced pa t 'lass l mad stair, s> spectra were recorded using me lata -/stem in a .-!.,:ed a,tn opiirjl isgoer separation using sass ::'!uny| Of PCOrs 6/ r.ofliloring eo'tcular OAS :ne tn- to actac.loro compounds Scjncsrdand rfer.e PCD[_ is Hen-: ane Poland, an. u 'tr. . I a n'.vrj; lar tne prest''. : .'Jr. 4as-Ja. Hcrinr.t/. :. i in 'able e). * : .1 Iwi order 01 fe 1 r.*,ZZf S I .3,3 .1 .0.1. ; - I. Tacit 2. Standard and reference PCOfs used in tlie present study 2,3.8-tn-COf 1.3.6.S-tetra-COf 1,2,4,6- 3.4.6./- 1,2.4,6,3-penta-COF 1.3.4.7.8 1.2.4.7,8 1.3.4.7,9 1,2.3.2.8- i 1.2,3,6,7 2.3.4,8,9 2.3,4.7,8l.3,4,8.92,3.4,6,7 1,2.4.8.9- 1,2,3,4,6.8-ftena-COf 1.2.4.6.7.8 1.2.4,6,8,9 1,2,3.4.7,8I .2.3,6,7.8;.3.4,6.7,6- :.3.4,6.7,8-Hepu-Ctf 9 10 11 12 13 H IS u 17 IS 19 20 21 22 23 24 25 26 27 6 (contains also 1.3 ,4.8,9-penta-CC?' d.b (contains also 1.2 .4,8,9-penta-wF > 6 (contains also 1,3,1.7.8-penu-COP ; 4 & (contains also 1 .2 .1,! ,3-penu-it-' C.f (contains also i , 1,1.6,7,c-ne:ti c.f (contains also 2.3,4,6,8->e f-'Z? t Dr N. Nonta. lotyo Neiro;aiitan Research ltborator> of Puolic ntaitn. Ic.,o, 0 Hr.8. undent. University of UaeS. Sweden; prepared tnrougn ;a i .a,cii-.a cjcluation of polycnlormated dipnenyletMr. *6 c Hr. 6. Carl, university of JmI, Sweden; orepered frcwi 3,/-dia' u.ujiLtn;-u<an acetylation. cBlennalicn ana reduction.1' a Or I Nesude. Oencm College of Pnarewceutical Science, fu-. . , 1 (Or. J. McKinney, Un-nel InstiiuU of invironnwnia 1 -cuicr s^ er Triangle Pan, K, USA . f - Hr Jar!. Uni.trsit/ uf ucci. Swccen. piepared n of peiycnlorinatea eipncnyietner 6 . - . i g - Or t Poland. NUrcU Laooritor,, Hadisor.. wise . US- HONS 003358 of tnninufMigntf.,,, Mid ii fett only very einor imuUs of edditionel isori r observed fci shgen in Figure 2b, the pyrolysis of 2,3,5,6-tetrechlBr90iphen*l lead Co cne form (i on of e tri-COf. The product eipecttd is I,? ,-tri-COf formed vie reeution route }. The fonunon of di-. tn- end tecre-COfs free this PCS _ie rsection routes I. ? end 4 is not possible end in feet no eddioonei PCDfs oere observed MONS 003359 CiL 220 uir- Mss iriff.i , 4~> 200*C -tri-CDFs is previously reported,10 t -t pyrslytit Of ?,6.2`.i`-t*trecli)orabipftenyl forced a Si* end a tn-CDf (e.ul.on of rthoK. m i gurt cc) ine expected ci-CC t tne 1,9- substituted HWr formed via reaction route 1. The fonaar.on of a tn-COf fraa IMS tetrachlorjbiphenyt hat t: -*vi!.* a rearrangement reaction; ttic itoner martio it i ,4,9-tri-CDf (reaction row; } i,. .)t PCfa cannot for* tn- end tttre-CDfs vm reaction routes 3 end 1, and ag i-.n nt additional PCOFs u*re observed. Pyrolysis of pentacnlorooipnen/ls The pjroly'it of fi* jmtitnlortbipnenyls 4t investigated (s* Table I) Hass `'agnentograas tnouiag tr.t ::,ii : o' t r-, t*Ka- ano pea-C0fs art given >n figure 3. Tha pyrolysis of 2.3.4.3,9-:*'i,*.nlorabijheyl ltd to tne 'oraation of a t*'.'*-CW at ta najor product and saallr' a-icnis of four tri-CDFs (tec Figure 3a). Tne '.ttra-COf eapectcd it us* 1,2,1.1-scott n.'rc soaer form*a na react.on route 3; tit* teat itoner at alto cbterved froa tit* e/roi/SH of 2,3,1 ,S- tetraLhlo-ubiphen/l. The formation of PCOfs v^e reaction routes !. < r.s i it not possible froa tr.it PCS !* finding of taall aMuatt of tri-CDft (Ould **en tie: ihett *C3fs ar* foncea m a non specific detrlar- 1nation process of 1.2,3.4-tetrs-CSf or of pdntecnlorobipeenyl prior to cyclwa.ion In either cate, the eipected ?CCfs contain Cl-substitueris delusively m on* of t" tuc carbon rings of tne <ioe*tofv<i' r-tleus 1* possible iseaers) "uo of these tri-Cofs *< tentatively identi f'.*d ... - 'i -C3T S , pyrulyt IS products Of 2 ,3 .a*0 2,3.i.b-teuachloroeipnc/i|i lie ri;.r* 2a and tj is snaan in Figure 3b. 2.1.3.2',: -pentatnlerobipiten/l 'omeo a eejnr i.'- .Lr ana smaller aaouats of 4 letra-CDfi a , pent*-Of Inis ntattr of PCOfs can 0* entered fraa the pyrolysis or this PCi ruction .outas I, 2, I and < (tee Scnuae be ,.j K0fs identifiee by co-cnroPet:?'*;', uitn reference .aapounds isee labI# 2| u*re 2,3.a trt- and 2.3.s..i-Wira-cfr . 'itm-a reuies I ana 2. respc.nvai,. So far. it a'- > v.. laen aade ' , , -< rtme.r.ing tetra-COfs 4 taall wuas of 1 - * eat wartN. a* < u rni 1. :.3 I.e.V- * la* ^4 * ' i >0* Tne pyrolysis of 2,4,S,3`.1'-pentacnlorobipheny1 lead to tne format iu. of to tel and a pentt-CDF (see figure 3c). ho tn-CDfs can be eipectad froa ims PC6 *_i_a reacd rout* 1. Ine Cue tetra-CQfs uer* identified by co-caroaetograpiy ;-n refert-itc coacounds (see Table 2) as the 2,3.7.3 and 2,3.6.7- substitutao Heart, forntj via reaction rowtt 3. This PCS cannot fora tetra-COft vja reaction root* 2 and in fact no additional tetra-COft uere observed. Pyrolysis of this PCS is opened tc for- i,,c penta-COFs >ia reaction rout* 4. neatly 1.3,*, 1,8- and 1,3,,6,7-per:s-CCF st $cnr beivu). nouever. only the formation of 1,3,*,/.8-penta-COF could be O' nr-a HONS 003360 a c'-(0)--(O>o '0 ?- Cl Cl 2367 |4o Cl Cl Cl ^0^ Cl^O^Cl U4.78- rs' pyrolyaed pm achloroO lpM dyl* shoriog oldttdn o f t r l - , m r * - and Pyrolysis of 2.4,6.2 .4'-pantacftlorohipMnyI ja.* 4 iri- and three ttra-C0Fi ai Worn ) Figure 34. tan wMr of tsodvrs cm m expected fron this KB u reaction rouiot 1. ` ar.; 3 (sv ^<hc<W Mlo* . t*i formation 'I a p-ate-CL* /ij rtacun. rot,'.* , ii iot possible ano in fact no penta-CDF mi ooservad, Iha tn-CQF Mpecied <1 the 1.3.?- substituted 1 toner. Two f tae telre*COFs were corftnMd a$ 1,3.6,7- ana 1.3.7,3tetri-Cf foraM rt:uio routes 2 *rd 3. respectiaely; th* thud tetra-Cbr 'first eluting) 11 exacted to he 1,3,4,?-tetr*-C0F, a" additional itoatr forowc *m reactior route 2 - c^^c, 0 (13.7-1 Cl Cl CI0^0CI C,07^>CI U&7- (1.3.4.7-i Cl Cl <3> a-Q&' 1.3.79- Tn* P/rolnn of 2.3.6,.:' -pencac'ilarooiphen/i lead to tn* for-aiioe of uo t j five tetra-COfi ssee figure Jti ai exptted fro* this PC0 ^a c t > -* n ru,,tes 1 l 3 (set Scftcac Mlix) Again, tn* fersauon or a pcma-COF >1* resc:i-n r0^t. ; t possible and in fact *0 penta-cc? *st ooserved. Cl Cl Cl Cl <D Cl Cl H3> Cl Cl Cl HONS 0033*1 Cl Cl Cl Cl 0-0 <dnp> "0-0 ct^o^ci ;i a '0^ (1.4.M-) <1.2 6.8-) 1.2.4 ft- ^ Cl Cl Cl Cl Cl a-- 0-0 d~h ^Q'-'ci Civ0'>Ti Dm of the M*n products Mt tentitieely idMtlfted u 1,2,4,8-tetro-COf, i pyrolysis product of 2,4,6,l'-tetreciildroor['.onyl#thdr * Too of tM tatro-CDf* (1,2,6.9* io 1.4.6.9- ) ire 1m tiptcud pyrolysis product! of 2.3.8,2' .3' ,6'-hoiocfelorobip*enyl (to* liter). PrrolyttS of honchlorotoipnenyls Iho pyrolysis of seven htaocnlorobiphcnyls wes investiqited (too Tibit l). Nit! friguortOfriM of pyrolyted staples *r qiven in ftSure 4. They skew the elution of tetri-, pent!* IM hoai-CBfs. TM rttvlti of tno p/rgifjti %f '.i.S,?',!1 ,4 - tM J,t,4,J' .1' ,l'->MKlilrl- biphenyl were previously reported.**^'** However, the identity of tone of the resultidq PCOFt m tentitwe ml coulo not ee cenftmod i( thit tine for lick of reference conpo'joot. Addition*! stindiros iviilikle nw aide it possible to confine these ttntit've identifications In cite of 2,4,9,2' ,4' .S'-nevichlorobohenyl. the fomition of i tetri- mo tuo poiti-Cjfs mi observed (tee nqure i'. These PCOfs uer* ioontifieo it 2.3,7.8-tetri*. 2,3.4,7,8- mo 1,3.4,7.8-penti-COF `onset vie melon routes 1. 2 end 3, respectively. I cite of 2.4,5.2'.4',6 '-heMChloroeipneoyl, I tetri- end pentt- COf were found (tee figure 4b) ina identified it 1,3,3.9-tetn- end 1,3,4.7,9-penu-CDf forma vil reict'on routes I end 2 The fomition of e penU-COf vj|_l reicticn route 3 is not pottiOle ith this Pcs tnc ' ?ct ** isoiuortl penti-CCF mt observed None of the Luo heaicMerooipner.yls tne-ed the foraition of s'qr.if'cmt mounts of heai-COfs. fry* tnt pyrolysis of 2.4,5.2' .4' .S'-no.ichlorohi.-nen/I, the fomtion of i nejor tetri- mo tom tmor oemi-CSfi ms observes 'tee fic^re 4c). The tetri-COf eapected it the 1.3,7.8- tubsti luted itoner fomed vii ruction route I. ;ne eapecteo penti-ffifs art 2.3.4.2.9- nd 1,3.4,7,8-peiti-CCf (miction route 2,. nd i.3.4.7.9-penti-COF 'reection route 3). However, oni, tn* fomition if l.J.4.7.3- sr,d I . 3,4,7 ,y-p*nti-C0f COulfl be confined. ;ne fomition or , . j .4,7.9-pcnti 3f reclined .reiser Tie pyreiytit of 2.3.4.2 .3 .4 -ne>|chlerobipnen..) Urn to the fomition of e tetrs- mo penti-COf (tee fisure 4d). iney -ere idet>fiea it J ,1.6,7-tetri- mo 1.2.3.6.7- per-.i-'Of. tn itowers e-vvi-ea -ron me p*-:ltn zf tru> kb io reiction routrt l mo ). 't-ecl..*l, '"e rte.l .`f. route 2 it not possible In -.nit iwaicnlorcbipnenjl 're lomiuoi of i nenKuf ,Oulj UC b uonhraa ."r p,rol,t n 6/ 2.J.i..1' .3' .5 I-roer*rer, l }** 4 a*10r ind 4 outer :elr|- Uf Uhd I Mjor penti-utf are fiS'.r* 4t; ine rijOl rCCft -ere identified 2.-.-.Sletrt- |M4 1.2 .4,6.8-tenti Cif . tne opoctec products frOa (HO pyrolysis of thlt Ki vi_. r.;,an routes I end 'ci^auci, fqnn. ine for itioa of i pontl-(tf m rtdction ruute . IS l-irt pdti lb It - 1 .' 'll, r.i . MU. !.' 1 HUlall is%.r j- absr rud. lied urcleir HONS 003302 OM -e itw d .. mu OCZ_________ u- 3^ Pit_________ t Pyrolysis cf 2 ,3.6.2' .3' ,6'-neaclorai Many! yielded Mm tetra* and two penUCOfs (tea Figure 4f), tM huomw of mar. expe-i, i *i reaum routes 1 -r.d (raaction route 1 amd 4 Mt posstbli for Wit FC8). In cate of tM tatra-tOfs, CM expected somers are 1,4,6,9*. t.f.S.** a> J 1.Z.i.f-tntra-CTf. Tna first two eluting isomers ear* alto obse>*M froi ere j,r^'-.it of 2.3,6.?'.i,'-pert4chiorQbipMfly) (tea earliar). TMrefore. tM last eluting tatra-COf eat tentatively identified as tM 1,2.2.)-sbstitwted isomer. lr. rata o' ta p*nti-COFs, the expected isoaart are 1.2,4,3.9* and 1,2,4,b.9-&er.ta-T,'f * a ' - at ion of 1,2,4,8,9-aerua-COf cowId be confirmed by co-cnromatogracv with a rtference sample (tee Table 2); tM ideetificatiee of 1,2.4,6.9-penta-COF at the first tlutir; isomer remains tentative. Tr.e Mjor p/roi/sis prafljc: -f 3. .5,3 ,4' .S'-newerio-oc B'.en/! ns iwnnfiad as 2,3.1 ..7.3-ne>a-COF itaa f'lurt ig). This ?CDF it formed ai reaction route 4. The rjr^a:ion it (tira- and panta*.3ft ,a reaction route, I. 1 <nj 3 it not possible for tmt ?CB isoear nevertheless. 3*jll woun-.s of pent*-C3Fs -are observed. but the identity and source of mate c . .- lined uncleer cCfe-4c. ----- Cl Cl 2.um- MONS Fyrolytit af hapta- and octacnlorobipnenyls Toe pyre: -f two hapta* *nd one oc'aLhlarobipftvnyl was investigat'd (tee Table I). ill tbraa isoaart art Min caapaaantt of nigMr chlonnatad coemmrcial PC3s.*' hats framantoqraat of pyralyatd taaplas art give* in Figure 5 The pyrolysis of 2,3.4.9,2' ,3' ,4'-hepUchlorobipMnyl load to the formation of pent* , hexa- and Kepia-CDfs (tea Figure 9a) A siegit penca-CDF it fomadi it was coafimeo at 2,3,4.6,?*penta-C0f, the a < potted product Iroa the pyrolysis of this PC* ia ran for rouse I. la case of tna ne*a*COFs. the formation of two itoaers was oesarveo mot coaplattly separated froa each other). The expected itoaers are 1,2,3.4.6.7- anc l,2,3,6,7,l"he*4-C0F ;reaction route J). The formation of the latter was confined o> COM>ariton to a reference sample (tee fable 2). In addition. Figure 9a snows tna e: .tic? of three hcpta-COFs- The Min itOMr was confirmed at l .2,3,4.7,B,9-npta-C0f, the product expected via reaction route 4. However, significant amounts of 1,2,3,4,6,7 ,- and 1,2.3,4,6 ,/,9-htpta-CDF were alto found. I he fomatioa of these isomers it unexpected but was to far not further investigated. TM pyrolysis of 2.3,4,5,2` ,4` ,9'-heptachlorobiphenyl again laao to the tarmticr. of penta-, hexa- and nepia-COfs (sea Figure 9b). Tna penia-CDf was confirmed as the 2.3,4,7,8- substituted itoemr formed reaction route 1. In cate of the eeta-O't. tr.t formation 0* tiro major and a minor ismr was obsarved. Ona of the major i^.-ers . confirmed as 1,2.3.4,/,8-nexa-COf, the amor at 2,3,4,6.7,S-nexa-CQf; they are pr.-:.::> formed vu raaction routes 3 and 2, respectively (see Scheme below). Trie other hexa-CDF is expected to be l ,3.4,6.7,6-nexa-CCF, another product expected \u relation route 3 Ini mss fra^sentogram also shows the elution of hupta-.'OFs. Tr.t -,w isr *> -as confirmed as 1.2.3,4,6,7,9-nepta-COf. the expected product from tins /'.i ,ia 'rat* . route 4 However, smaller amounts of additional tapla iOfs were also ,cer,,.e J1L o^do Cl Cl ct 0 2jw?a- 3363 <3>CI*@'"^C1 ZAA t c} UU- a a a '-07-0* cr^o^a Cl l Kd - 1M . JJ*. 406 and *40) of pyrolyied M o tt- and octacMoroOtpNMiytt I having elution of IM pyrolysis of 2,3,4,S,2 ,3` ,4` .S'-octacAlorebipfteny) yielded ha**-, hOU- and or ta-fOfs (** f i i.re St) The n*i* l*>*-CDf <**a confined a* rn 2,3.4,6,'.8Subttituted imr forced via reaction rout* 1. |a addition, a ainor heia-COf *4$ also observed. the identity *n4 source of uhich rwinad unclear. Tke hepta-COF was confirawd at the 1,2.3,4,6,7,3- substituted >softer, the eipected product forwed v_i* reaction route 3 The aass fragaentegraft also shoos tha elution of ocU-COF, the pyrolysis product fonwd vja reaction route 4- The pyrolysis of 18 individual KIs uas studied and sfeoon to result it the foraatiyn of PCOFs m intramolecular cycl nations. Tne yields of PCOFs *ere estimated to be in the range of O.JV up to several . Again the application of high-resolution GC and MS is dotkanenttd as a ntcassity for the separation and identification of tn* PCOfs for^o. Pyrolysis of individual KIs has proven to be useful for the preparation of iniji.idiml KOfs in situations uhere only ainuta founts of isoaers are required for reference purposes, Mainly in GC-NS analysts. Ihe formation of the KOfs uas found to follow four general reattion routes involving the less Of Cl^, Mj, and NCI with or uitnout a 2.3-cni me eig-ciou ,.r. introduction). Ouc to the observed generality, it is possible to preeict tne structure of the resulting PCOfs. The results support our earlier conclusion that pyrolysis ol FCBs is resulting u tne formation of highly toic compounds uinsequently. the uncoatrcHeo C.rmng of Pits is a threat to the environment ir.d sneuid be avoided. Acknowledgements ut thaM Nr. A. Gart and Hr 8. Linden , Ors. k. Andersson, r. ;ias-ji. j ftn.rnt,. Nnrita, A. Pc I and and C A .ackteaister for making avadaola the PCSs ku me ?;ct reference caapbundt used iu the present investigation MOMS 003364 Nai fregaentegreftt C. Raope, H.a. 3uit' a?: P Sojnjr3t, Ana. dew fort Acad. So.. in press. 2 A Poland( . non' . -. . "CJ. : B 01. Chap.. 2Si. 4936 j 1976;. 3 J-A. Noo>*t, E.E. FtcC&nrti: . if. a. Gaiiard and K.V. mrm, Ann. hew tort Acad. Sci. in pry;s 5. H. Auroll * 3 i. Has.;i. i-uly-ari. 7. -71 (1978) i. H.8. SuStr. C. itap^cr a-a . ierS. CMTOsatier^. 7. (39 (1978'.. 6. C. Rapp#, A Carl and - *. Bvter. Cherosphere. in press- 7 C. ftappe, h R. iuiar i't - -P ootshardl. Cheaotonert. 7. 431 11978). 3. J.G. Vos. J rt. Aoeaan, r.L van der fleas, M C. ten Roevtr de Brauw and R.fi. de Vos Food Cosaci id'ICOl . i. 2i '})70i. 5 It. Olie, F I farmvltn ar i 0 lucmqer, Cheaos^nere. 6, 4S3 (1977) O. h.R. 3uter, n.-P. Botsrar- . C. Raoo* and fi. Lndafii. Cherosohere. 7. 419 !)978). i' Dmr Cneaua Co'jan/. Tf__ "rac* rnenistrir* a# Fire. Report. HoerCer. 197b. 12 R.J. Satin, sci>, i2i. lie (1976, i 3 - M.R. Buter, r. -A Ssssrir: andC. Rfspe. Chenoicnar*. 7, 109 (1973) i. A itori ca. j .4aS4-a. -iviCie. i Ri-.r} gns Ll'llii' *J . 6> '1977 i M Horita. . M-d9*-4 I' .. if.:-, -ui; m, (H/l is?-3. Soil Emiron Coniea :ol . -:6; c. I. Mcrslrpa K. Anders.-' id - as. Cftanostrcere. 5. 419 176). 7. as r.enoe. J.J waJt " of tr-e -in. Cre- V' n * :.sr. 0 4id$e and * Poiand. left* lauanal Ktettne rj. L1* ..c-:-;y " A. i.cser . i?7i (Received la Ok Petnury ;i". MOWS 003365 ENVIRONMENT INTERNATIONAL A Journal of Scienca, Technology. Haahh.Monitoring and Policy Previously announced as International Journal ol (he Environment eu.wi A A Moghiatr U S in. -rontnant* Avracnun AafCy ftaUunqtan O C . U S.A U>q>nggOiior llrtolllt^Mti Conanu o4 VoNmm 1 NwiiAn 3 SPECIAL UNEP ISSUE FOR WORLO ENVIRONMENT OAV Oimk Eii.iwi MewetR Sn. ,nj Am B. Iiimi MK TOlBA |.u.:.,r>rl:- y fnK/Oiirtte/tf Pry^rj i-' c \j.r-v-. FlrniMd ' UARGAflt I r a 5.-; BISWAS Anna, J Canaria Edrlonaf AJ| T HtPOFiT OF /Vjf.u/rl C|>k./u/iw if Environmental li-maci of l-fno**! WMluJ Owof Natural Anourcn REPUKI OF iHf lt _T1 t Oi-i I AWrufu <w.jf ' ' ** ThaStaW el OW fcn.<MMni Set*-KJ Topw> - lira MK !0HA r... ..... (6winyiifA,/ c (anoMMi MaAu^aiant . ' ' UNSPSEuRiJ-lH.-tr EnvMonmoAi and Oavetowowni For inMjnct 6i:n ilk> ...u .*i HMlIx MMulml, SuMCfiRbon InlfMiixiiur. *wOuWclO-....... .. Transportation Committee. Both committees have juristic* lion over the superfund. Breaux said that Uie liability provisions in the superfund "should bo interpreted narrowly" to cover only third party damages for economic loss, not for medical injuries. Breaux said that he agreed with the Administration's proposal not to award third party damagea to victims of abandoned hasardous waste stlae bacausa soch claims would drain the super* lead. Poe Net A Penafty Regarding industry assertions that the let asstssad gainst tha potroleura and chemicai iaduatriea to finance the --portend Is unfair and 1> a "penalty" for part disposal prac* Ucos, Breaux said that bo does not regard the fea as a peaeity, but rather ae a fee on a product Ho said that la* dnstry can add tha fae onto the cost of its products, ul timately paaaiiif tba added coot oa to the consumer. In addition, Breaux said ha did not agree with Industry assertions that tha liability concept In the superfuod Is an ex poet facte denial of due process. Utffedos - U.S. SUPREME COURT TO HEAR BENZENE ARGUMENTS OCTOBER 10 The U.S. Supreme Court will hear oral arguments October 10 ee the validity of the Occupational Safety and Health Ad* ministration's standard governing worker exposure to The arguments before the Court will com* more then a year after the U.S. Court of Appeals for the Fifth Circuit truck down the standard on the ground that OSHA failed to show that the standard's benefits bear a "reasonable relationship" to Its costs. OSHA end the AFL-OO, both of which are seeking to have the appeals court decision overruled, attacked the conceptof balancing coots against bandits in ratting an exposure level for toxic substances. Oil.producers and users who successfully challenged the standard la the Fifth Circuit Court accused OSHA of ex aggerating the appeals court nritag. The producers and users Insist that the court did not require OSHA to conduct an elaborate cost-benefit analysis but only that it consider s "rough but educated estimate" of bandits expected from reducing the permissible exposure level from 10 parts per million to one ppm. The Court scheduled one and a half hours for argument of CHEMICAL REGULATION REPORTER According to attorney Doane Miner, the suit is the first one filed by an Occidental employee against the company itself. Worker's compensation laws prohibit a worker from suing bis or bar employer for work-related Injuries or illnesses. But the attorneys for Arnett said that recent evidence, which indicates Occidental knew DBCP was in the drinking water supply of the plant, but did nothing about it. provides cause for action against the firm for Intentional and willful injury. A high rate of sterility among workers at the Lathrop pleat was first discovered in September 1977 end resulted In the Issuance of an emergency temporary standard by the Oc cupational Safety and Health Admlnlatratioa (Currant Report, September 16, 1977, p. 999). Arnett charged in his salt tint Ms DBCP exposure coined his sterility, which was reversed when the plant ceased manufacturing the pestldde. The complaint was filed as an amendment to an earBur suit against several chemical companies and rssaarchsrs which alleged tha defendants failed to pwhllctae their research on the harmful effects of DBCP. Spokesmen for Occidental Chemical said they had not yet been informed of the suit, and tharefore had no comment. Haaardoua fubatancea CHLORINATED AROMATIC COMPOUNDS SOURCE OF DIOXINS. FURANE IN COMBUSTION PROOUCTS raratrcnenT"' mis nnoinji was reported by Chrlstoffor Rapp*, of tie University of Umea, Sweden, and Hana-Rudetf Bauer, et the Swiss Federal Research Station, Waedenewil, BMtmtoed, during the American Chemical Society misting held In Washington, D.C., September 9*14. are similar in chemical structure and toxic effects to the dioxins, but ere somewhat less toxic and have received leas attention from environmentalists and the public. However, Rappe told Chemical Regulation f Utlgstlow OCCIDENTAL EMPLOYES CLAIMS DDCF CAUSED CHILD'S DEFORMITIES An employe* of the California plant which manufactured the pesticide dlbromochloropropene (DBCP) filed suit gainst the company charging that his exposure to the chemical causod his child's deformities. The action, filed August 28 by attorneys for Frank Arnett, an employee of Occidental Chemical Company, Lathrop, Calif., charged Occidental with "carelessly, negligently, and recklessly" falling to prevent employees' contact with DBCP, allowing Arnett to became seriously Injured. The suit asks more than $6 million In punitive damages and IS million In compensatory damages. largely of the less toxic members of the dfoxto farafiy. Rappe raid one study Inmcata test 2,3,T,9*tetruchter dibenzofuran (TCDF) Is about one-fifth as toxic ae 2,9,7,8-tetrachlarodibenso-p*dtaxln (TCDD), the most toxic of the dioxins. Rappe end Buser recommended that the burning of PCBa and of chlorinated phenols, benzenes, and diphenyl ethers be carefully controlled by monitoring chlorinated dioxlnj and furans in fly ash and flue gases. PCBa The researchers said burning of commercial PCBs was found to produce a variety of chlorinated LnKJtiuifltl ol Mia rail J iflfl irpercratL They said the most fnraa S-14-70 CtwmteW Regulation Reporter oua ren'wsoow HONS 003366 ^current Report $$ ------------------------------------------------ - irDF. wax i main constituent of the fursns oroduced (ram .v fast---------------------- ------------------------------------- ---- Rippt said the pattern ot isomers formed Irotn burning ' pcBs showed a close match with the pattern found in fly ash samples. He concluded that uncontrolled burning of t- materials containing PCBs may he an Important source of -V. bssardous furans in the environment. The researchers alio said hey are Important precursors to dioxins bund In fly aril. This finding may have serious Implications for the future statua of panted)lorophenoi, a common wood preaervatlve which la currently being reviewed by the Environmental Protection Agency lor posatble regoletory restrictions (Current Repart, May la, p. US). Ml waterway, came from original production of tbo chemical rather than from Its use in industrial processes. Stalling said the level of furans in manufactured PCBs i$ PCBa end Ofoxfn Initial Interpretation of the now data showed that there ia lilllc relationship between PCBs and dioxin formation. Suit ing said. Dioxin, for example, was found In the only body of walar where no turan contamination of lisfc was found. Stating said. Tlte data presented by Stalling was found by totting Mfish samples collected at five sites between iglft end im. Hu said 25 to SO more situ* win be tested tor furans in the can* tog year. The adentiata also said chlorinated furana are produced from comhuatlon of any o( the varioua chlorinated dlptaqrl ethars. In addition, thqr uid, aome of the ethars alao yield vuj^^moOBUddtoitoojDchidtafTCDtt ..................... ni at lowers Rappe and Buaar reported eaparlmenta with a variety of lira raiardaat diemtcale. They said a Dumber of the chemlcala tailed jrieldad dtoxtna or brans. Ono name rttardant, haaahnmehlplianyl, yielded 1 to percent of the moat taab tana laomar. The* raceramended that halagenatad phanola, btphaoyla, ind dtphewyt ethers should not bo used aa flame retardants. la a related development, nvts I- in ef the UJ. Ft* tad WUdlUo Service's National rtiheriae Research lug said the fsrana have been detected at leveta of ahoet one pwt per bilUsn la carp, catfish, coho salmon, and lake (root tehee from the Connecticut. Hudson, and Ohio rivers, and Salting related um (lading of brans In fish to Rappe and Bunt's discovery that lunua are created by comhuatlon ot .am-wp* .a Manama a.fade.. be done baton any milled. _ and In* I or incineration of PCBs la | Stalling aald farad levels In fish taken from the Hudson River were lower than the levels found In Osh from the other wttarwayt. He said much of the PCB found In the Hudson, **leh la believed to contain more PCBa then any other U.S. themselves against consumption of furans by tofiowtag advfsories against consumption of fish token from waters com laminated by PCBa. No Dloxfcte Prom CoofcPItod Power Plane The amount of dioxin to particulate eadaatono front eaa^ fired power plants "Is so small as to escape detection with the finest scientific equipment available, UJ. researchers said at a September 13 ACS pram ronfsrenca. Brenda Kimble, of the Department of energy's Radtoblolofy Laboratory, and Michael L. Grom, dfrocteref the Midwest Center for Mam Spectrometry, at the UWverst ty of Nebraska, doscribod thoir analysis of fly aril pnrttetes collected from tho alack of "a typical power plant b--atog low-sulfur, high-ash coaL" They said they found no ttioxto at tho lowest levolof detec tion, corresponding to ono mHttooth of a gram of TCDDfrom the burning of 200 tons of coal. They contrasted their findings with results reported by thu Dow Chemical Company. Dow researchers found dteuteu to emissions from a wide variety of combaettoa sources, including tosrii-toeled power plants (Angari 31, p. Ml). Kimble and Gross suggested that Daw's candwtena control be applied to all toeaU-faelod power pterin. Donald Townsend of Dow, who was also present at thu press conference, said the power plant tested by Dow lad burned primarily fad oil, with a small ameuat of caaL He said Dow had found dtextosalt over the Midwest, Tow--end arid dioxins, including TCDD, wore even found to a U.S. Bureau of Standards itandardtoed sample of urban par ticulate matt--. Gross Mid ho would not want to extrapolate Ms fiadtogi to all power plants. Including thorn not barring western cent. Baser said the European researchers bad nut studied emissions from coal-burning power plants, atom cool to nut used to generate electricity to Swltsertond. SterHify-JJnkad by Weeewohei m PCBo Functional sterility significantly correlates with the level of PCBs found in human males, according to Ralph C. Dougherty, a Florida State University (FSU) resesrch chemist. He said 23 percent of the males he tested were functionally sterile because their seminal fluids contained lew numbers of sperm. The lowest sperm densities were found to mm with tho highest levels of PCBs in their bodies, Dougherty said at a September 10 ACS session. Copyright 1979 by The Bureau of Nettonel Affaire, Inc. oi4e.*n/7soe9e MQNS 003367 4a * CHEMICAL REGULATUM 'ORTE Since 1974, thcrt hM bee* a greater than IN percent in* crease in the number of males with low sperm densities, in dicating functional sterility, Dougherty said. His research shows that PCB contamination accounts for about as percent of the shift toward lower sperm counts, he said, adding that he believes other toxic substances eventual ly will be Implicated In the decline. Dougherty said Ms study of 132 men at FSU showed that 23 percent were functionally sterile because they had sperm densities of leas than SO million per milliliter. hi a I9M study, only about 7 percent of the man tested were functionally startle, while, in 1974, about IQ percent were, Dougherty's statistics showed. . __ Dougherty said several Identified toxic substances were found In the seminal plasma of hie volunteer*, but that only PCBa correlated with lew sperm densities. Among the substances found, but net tied by Dougherty to sperm density, were pentachlorophonol, haatacMorebsmane, and various metaboutas of DDT. He sold sotno ether chemical* found correlated with the lew sperm dtvtK*--, bet that he and hie coworfcers ware un* able to Identity the eubetencre. None of them, however, seemed to have the significant correlation which PCB had, Dougherty said. FwiMiy Piilwlm Dougherty said median sperm density has declined from 90 mUUen per milliliter in 1929, to 95 million per mUUUtorln 1974, and to 90 mOlion per milliliter In 1979. The most common sperm density found in volunteers, however, illustrates the steep decline la the fertility rate, Dougherty said. Ptotttng the sperm densities on a graph shows that the largest numberof men la the 1929 study had sperm densities of 109 million per milliliter, according to Dougherty. la 1974, the largest number of own had a density of <0 mtlUon par milliliter, while In the 1979 study, the most com mon density had fallen to 20 million per milliliter, Dougher ty said. The refeercher said he believes cottage students mayhave lower than normal sperm densities because of sack factors as stress and sexual activity. He added, however, that the lower densities found In Ms study could not bo accounted for by the makeep of tho study eroua alone. To validate his study, ho has recruited a number of workers la an electrical plant Because these workers have keen sxpoaad to PCBa on a regular basis in their jobs, their sperm counts should confirm Ms findings with cofioge For that reason, evaluation of sperm const and tnrfnal plasma could provide a method of correlating Impeded cell division with the amounts of toxic substances in the donor, he said. Those substances which seem to bo lowering sperm count should be considered too hazardous for use and should be banned, he said. rCBs Increasing in Qreet Uhw The contamination of the Great Lakea by PCBe may can* tinue to increase in spite of tho EPA boa oa fortbsi produc* Uon or uso of the chemicals, research** tMd ACS September 11. The researchers said the atmosphere la the major source of PCB* presently entering the lake, and Tlwnfnre. the reu cannot be prevented by illmmemg mamdpal and industrial discharges of PCBa into fee Has. DDT. Ho said DDT levels In fish declined rapMty after tbs pesticide was banned. FVesent concentrations of PCBs fat maw Bab cscood the Pood and Drug Administration limit of ton parts par million, Murphy said (June 29, p. 471). FDA cecaatty stayed the now two ppm action level (Angret SI. p> WO). Murphy said known poUutloa from manldpM, Industrial, and tributary sources do not mem to aeooenllirlhnprennt PCB levels In the Greet Lakes. He sted he and atom researchers set out to determine whether faNrelfreae toe at* mosphere could be an important source of PGB ceutemfcation. They measured rates ranging from 19 to 751 square kilometer per year at varl-- ptoie In Lake Michigan and Lake Horen. Assenting an avenge rate ef 25 grams per square kilometer, 1........................ of PCBe from the atmosphai Murphy said the PCBs in the itmnephsre pnhohty come from such sources as municipal toetaarators and svepsrs Uon from landfills, from PCBs discarded in Am post, and from PCBs used In paints and ae p " S. J. Eisenreich of the University of Mfaaanta reported research on PCB contamination of Lake 9qekr. He seM atmospheric deposition from rain, parttdn*, md PCB vapor account for over 89 percent of the total PCBa presently entering the lake. Eisenreich estimated that HlJHH nrtM-Irti to 3,500 pounds are removed by i mentation. Consequently, 15 thousand to 219 apparently accumulate in the lake each year, be said. Slgnlflenneo to Conof Study Dougherty sold Ms study has major significance for detectinghasardoua substances and for carcinogen detection programs. Because it takes eight coll divisions to create a sperm, a lowered yew count shows that something is Inhibiting cell division, Dougherty said. Most substances that alow cell division are found to bo car* ciaogonic or mutagenic, he said. towel Hoo Not Poshed Eisenreich said be believes the atmosphsrte contamina tion of Lake Superior has not yet reached its peak, although PCB production has been dropping since 1959. Ho said PCBcontaining materials and products such a* electrical equip ment are being disposed of continuously. He iaid there is a substantial time log between the disposal of PCBa and their appearance In the Great Lakes. Elwnnikh width. Import**, of .Inxayhwlc twHim as a source of PCHcreuminafionirWIlBto****** nw t^T 0-10-71 Chemical Regulation Reporter ei4t773/7SSOOBO MONS 003368 CURRENT REPORT 943 Utigotton He Mid lisa caught In the island lakas had PCB lavtlt at much as 100 tlmu higher than (hoe* caught in the Great Lakes. He attributed the higher contamination levels in the Maud (tab to the shallowness of the island lakes, which makes them more sensitive to atmospheric contamination. Eisenreicb said the Great Lakes have low sedimentation rates. PCBs which settle out of Um lake water remain dose to the surfact of the bottom whoro they art ovaOablt to hottonvfceding merine life, he said. He estimated that It would taka about ITS years for PCBs to bo beriod In aadimenta so deeply that they cannot reenter the lake. COURT PARTIALLY BARB CLAIM AGAINST ALLIED CHEMICAL IN KEPONE SUIT A former officer and director of a Virginia firm which manufactured the pesticide kepone was partially barred la his attempt to collect damages for emotional and defamation from Allied Chemical Company, which con tracted to buy the pesticide. The U.S. District Court for tho Eastern District of Vlrgkda, in William P. Moore v. Allied Chemical Corporation, Tho Travelers /ndtmttilp Company, and rfneflsr Chemicals 6 Plastic Corporation, doteradaod that Moore was barred In tho smofinml iflstTsss iltlin bntconM proceed in Ms defamation suit to rseovsr damages. ability to carry pesticides and PCBs by up to 100percent, ac cording to John Duck, a research rhemtst with NUB Cor* porktion, Pittsburgh. Pa.. While the findings menu bacteria la drinking water may post a graatar health bassrd than originally thought, they alao moon that bacteria could bo end to removo hazardous Duck said Ids rasaarch shows that tho preaanca of bacteria In water lecreasts the amounts of psstlchtea and PCBs that tho water can hold. The chemicals sewn to attach thsmeslv to the can mem- feraaoo of tho bnctarte and am r--latent to removal, Dock Moore's former company, Lite Science Products, pro* dueod kepone purchased by Anted. At iseee wne whothar Moore had an opportunity to litigate the matter totiy dmhm Occupational Safety end Health Review Camodstem proceedings following an Inspection of tho Lite Scteneo Products. Hopewell, Va., plant August U to IS, 1971 Allied contended that admissions in tea Jbnrnr miywf-- prohibited Moore from alleging that he was wum af tea foil dangers of kepone and thereby panting Mb dofmo against Allied. Moore mnfndsd (hot AMsriamw of the devastatingphysiological tffacte which kepena eould kovoeo Ids workers, but that the firm deliberately failed to um him of then dangers, and that, rnnsn|usti|j. ha saffored severe emotional dlitreo. Tho bnpUcatiem of tho itady am ttaft pesticides, PCBs, In determining that Moore was estopped an the emotional f and peoribly athar toxic snbatancaa could be removed from distress coontrttm court adopted AIUod*s argmoont However, as to the defamation claim, the cosrt found that coated platae through the water, Duck said. Ite rmarcbir said ha found that bacteria form a major tho facts and issues determined iatheOSAHRCproceedtegs were not substantively the same. Writing for tho coart. Judge Calvitt Clarke, Jr., saM tint the truth of Allied's statements and their defamatory notore Without tho bacteria, tho PCBs and pesticides toad to set* were matters to be determined el trial. tie out of water or tend to be adsorbed. Deck sold. Bacteria, along with tha attachad haxardout substances, tend to remain smpanded in the water and am difficult to filter ant. Duck sate. He said that he found destruction of tha bacteria cell had little effect ea Its ability to bold tho hasardous substances. Pesticides ROHM ft HAAS ASKS EPA TO CANCEL REGISTRATIONS OP VACOR ROOEMTtClDC Tho chomtcals tested, aMrin and PCBs, seem to attach to the cell membrane or poestbly to combine with the lipoproteins In the membrane and thus am resistant to destruction, he said. For that reason, chlorination or other means of sterfllsa*- Uon do '*not necessarily eliminate'* the potential hasard that ftntehad drinking water sappUae aright contain PCBs or poaUddoa, Deck nM. Dock said that filtering the watsr may remove some of the bacteria and consequently tha haiaidons substances, but that mom tasting needs to be dooe before a definite Judg ment can bo modi on tho effldoncy of filtering. He told further work will be done to determine the exact method by which the bacteria carry the hazardous sob* stances and to find eut the feasibility of using becteria-laden pistes or membranes to remove hazardous substances from Ho said hit study has significance because treated drinking water contelne between 100 and one million microorganisms par milliliter. Those microorganisms, which am resistant to normal treatment processes, serve as convenient carriers for hasardout substances, he said. The Rohm A Haas Company vohmtarily ripiital that tee Environmental Protection Agency rural U.S.restratiom of its ret end mouse pesticides contaioini the active gradient Vacor (N-3-pyrjdylmethyi-W p titrophsnylwta), the agency announced SepUanber 12. Tha company said it stopped sate of tea mdaatiddm worldwide and has began a recall of the prodmte, according to tho agency. EPA was already in the preeese of reviewing the registrations of Vbcor because at concerns espreaed by dm California Deportment of Fbod and Agriculture, which bemad the rodenUdde for home use March 1, tea sgsney said. Vacor has been the cause of several hum-- deaths In Ssnlh Korea, most classified as stickles, EPA said. Gitifomln reported nine adult poisoning casts, two of which romltad In death, the agency said. California was aim comsrnsd that tho packaging of Vacor products appeared to be attractive to children, according to EPA. The products involved were sold to consamsra under the dame "Vacor Rat Killer" and "Vacor Rat and Mourn Killer," and to pest control operators as "DLP*TtT House Mouse Killer" and "DLP 787," the agency said. *14-70 CopytWn 1079 by The Bureau of National Affaire. Inc. OI4t-7973/7WSOO 90 HONS 003369 Page 2 gjSgfe 7bU, Wm, ^ST'CIDE fi TOXLC^EMICAL NEWS into a cocked hat last week when U. S. Fish & Wlld^^^scTentls^Dr^avid Stalling reported at the American Chemical Society meeting that polychlorinated dlbenzofurans, 1,000 times more potent than polychlorinated biphenyls and a probable carcinogen and teratogen, accompanies PCBs and Is often masked by the parent chemical. Meanwhile, EPA officials were at Midland, Mich., this week receiving part of the Information the agency subpoenaed in connection with Dow Chemical's pro duction of monochloro biphenyl (See Sept. S, Page 10). THE WHITE HOUSE Regulatory Analysis Review Group, established to make certain that government regulations make economic sense, has so far left TSCA Implementation alone and has not commented on any TSCA proposals. E PA SCIENCE ADVISORY BOARD'S subcommittee on toxic substances will meet Sept. 19 at Waterside Mall to review health effects tests standards proposed by the Office of Toxic Substances. H EX A C H LO RO CYC LO PENTAD IE NE was Inadvertently left off of the list of chemicals for which the Interagency Toxic Testing Committee recommended epidemiological studies (See May 16, Page 27), EPA corrected In a Sept. 4 Federal Register announcement. EPA'S JOAN Z. BERNSTEIN , Office of General Counsel, will serve as Acting Assistant Administrator for Enforcement until EPA finds a replacement for Marvin Dumlng. Swep T. Davis, formerly Deputy Assistant Administrator for Water Standards and Planning and James N. Smith, formerly a Special Assistant to Thomas C. Jorllng, have been appointed to the positions of Associate Assistant Administrators for Water and Waste Management. Davis will focus on strategy development and "superfund" while Smith will work on pro gram operations. E PN RPAR NOTICE Is scheduled to be published by EPA In the Sept. 19 Federal Register with an Oct. 29 deadline for filing rebuttals. The deadline will probably be extended to early January. The RPAR Is based on delayed neurotoxicity (See Aug. 29, Page 21). HOE LON 3 E C , dlclofop, (See Aug. 1, Page 2) slides from animal studies were scheduled for a side-by-side review Sept. 12 at a meeting of EPA scientists. Dr. Melvin Dwalne Reuber, National Cancer Inatltute-Frederlck Research Center, and scientists with American Hoechst Corp. It Is understood that Dr. Reuber's earner review of the slides noted carcinogenic effects. NOTICE that Mobil Chemical Co. has applied to the EPA to register Hefty Dog/Cat Repellent containing 16.4% of the new active Ingredient cinnamic aldehyde was published In the Sept. 6 Federal Register. The company proposed the pesticide be classified for general use to repel dogs and cats from garbage bags and cans. Comment deadline is Oct. 9. PESTICIDE PETITION filed by American Cyanamid, and noted Sept. 6 would set tolerances for residues of pendlmethalln of 0.1 p.p.m. In or on sorghum grain, fodder, and forage. The herbicide Is N-(l-ethylpropyl)-3,4-dlmethyl-2,6-dlnltrobenzenamlne and Its metabolite 4-((ethylpropyl)amlno)-2-methyl-3,5-dlnitrobenzyl alcohol. EPA on Sept. 4 made further editorial changes in Its alphabetical list of pesticide chemicals (See July 11, Page 5), deleting extraneous listings and adding those that were Inadvertently omitted. HONS 003370 Page 22 September 12, 1979 PESTICIDE & TOXIC CHEMICAL NEWS applicant relies on Monsanto data either by "clte-all" or specific reference; notice to compeny and to above named law firm,1 registration cannot be Issued until 20 days from the date of the notification letter; the requirement does not apply If the applicant submits his own data cr data other than Monsanto's to support the application or is authorized by Monsanto to use Monsanto's data. The Diamond Shamrock stipulation procedures Include: (1) above with 30 days notice to the company; registrations cannot be Issued until 3S days from the date of the notice letter; and, essentially (4) above. The Merck and Company, Inc. stipulation procedures Included: 30 days notice as In (1) above to the company's counsel, Patrick M. Raher of the law firm of Hogan & Hartson, Washington, D.C.; registration cannot be Issued until 35 days from the date of the notice letter; and, essentially (4) above. Provisions of the Petrollte Corporation stipulation compliance procedures: 15 days notice of Intent to "register any product or accept an amendment containing alutiraldehvde as an active Ingredient If the product is labeled for use in oil field operations" sent to Raher, Hogan & Hartson as above; registration cannot be Issued for 20 days from the date of the notice letter; and, substantially (4) above. In complying with the provisions of the Injunctions and stipulations, the Registration Division will find all registration actions covered by them on ever-changing lists, In form the applicants, tell them how to comply, wait for their response, notify parties to the Injunctions and stipulations, wait for their responses before acting. Delay and Fish contaminated with polychlorinated dlbenzofurans (PCDFs), a by-product of polychlorinated biphenyls (PCBs), have been found In the Ohio, Connecticut, and Hudson rivers and Lake Michigan, near Saginaw, Mich., a federal Fish and Wildlife Service reaeercher reported Sept. 10 at the American Chemical Society (ACS) national meeting In Washington, D.C. (See Page 2). Dr. David Stalling, the Interior Department researcher, said PCDF can be formed by the CKldatlon of PCBs, especially when they are burned at relatively low temperature. "Weknow that very high temperature burning. If done for long enough, will completely destroy PCBs," Stalling said. "However, Dr. Christopher Rappe, University of Umea, Sweden, has demonstrated that low temperature combustion in the 400 degree to 600 degree Celsius range can convert 25 percent of PCBs to PCDFs." The PCDFS, at concentrations up to 2 parts per billion (p.p.b.), were found in carp, catfish', lake trout and coho salmon In areas where there has been a historic problem with PCB contamination. Stalling said. "We have not yet Identified the Individual chemical structures of the PCDFs In our (fish) samples," he said, "sa we cannot be sure which of the 135 possible compounds are present or whether they might have toxic effects. " "Once specific PCDFs In fish are Identified, laboratory scientists will have a better Idea how they are formed, and which structures should be tested for possible toxic effects in fish and other aquatic organisms, " the USDI researcher concluded. HONS 003371 lienee state continues over boss's dioxin theory sub ol Mvsral recent tflee don't JKm with Dow's itantton that dioxins sntsr <>cnment from combustion; I, agreement is emerging 1979 I Washington, D. : kins mitahoti at Dnw Chtmir.l'j at** tnt poivcfllorinatad di- iTTOWlM juri formeo py ell iikfcrt.uAiouitouliin thnviro^; ttOMjnVlWn Tfiere are reporters Mat Tht most recent opportunity this activity, the symposium end sea conference on the cnemiatry of wntudloxlns and dibenzofurans, uneereri Jointly by the divisions of stickle Chemistry and of Chemical .'nlth & Safety (Probationary), had ahaie of shooters. But the sessions o seemed to show, perhaps for the st lime, an emerging common tund shureri by scientists on all `es of the issue. The issue is Dow's theory, first posed lest November, that poly'orinated dibenzo-p-dioxins, dituofurans, and biphenyls are med in trace amounts in ail forma combustion. Therefore, they are t only ubiquitous in the environjtfULtM have been there since the vent of fire, (t is only their detecm that is recent, due to udvances in mlytkal techniques (CAEN, Feb. VBSSv has gained so much at- ntius because one of the polychlonaled dibenzo-p-dioxins, the l,7>tetrechloro species (2,3,7,8* CDD), ie an extremely toxic cmn>und that also is a carcinogen and a ratofen in laboratory animals. This mpeund is a trace contaminant in i herbicide 2,4,5-trichlorophenoxicetic acid (2,4,5-T) produced by ow and others. T.h. herbicide is currently under an emergency suspension for many uses | from the Environmental Protection * Agencv because of an alleged associ- J at ion between its use ana increased 2 miscarriages in a group of women 3 living near forests that had been sprayed with the herbicide in Alsea, Ore. Detectable levels of 2,3,7,8- TCDD also have been found in fish taken from the Tittabawassee River, which flows by Dow's produc tion plant for the herbicide in Mid land, Mich. Presence of the com pound in fish led Michigan's De partment of Natural Resources to suspect the compeny of illegally contaminating the river with this compound. So Dow's theory that combustion is a major source of polychlorinated dioxins in the environment is more Crummatt: compter and oxpomfvo than interesting chemistry. If true, it goes a long way toward absolving the Evert these reports may be at least company's product and its manufac - partially compatible with Dow's luring process from responsibility for findings. For example, Warren B. contamination of the environment by Crummett, a research scientist with these very toxic compounds. Dow's analytical laboratories, ex Among the potshots the theory re plained that the power plant where ceived at the symposium, two are Dow found dioxios in the stack most prominent: Brenda J. Kimble of emission* was on Dow's Midland fa the Department of Energy's Radio cility. During the sampling period it biology Laboratory at the University was burning primarily fuel oil, with a of California, Davis, and Michael L. small amount of coal. Various scien Gross, director of the Midwest Center tists at the press conference suggested for Mass Spectrometry at the Uni that possibly the fuel oil, or even the versity of Nebraska, Lincoln, have air in Midland, contains chemical aatlyy.ixl the smokestack emissions of precursors to the dioxin* found in the a cnal-firea power plant in uaMorma. stack emi- ions thal are not found in TUflV fUlfl nn 'lCDLI'l In Iffl Emis the California power plant. sions. down to their detection IpvpI Crummett criticized the California U b pm i'lb mT,. The Ouw study study in two wa>3. He says the sam looKeq specifically attne smokestack ples were taken from too low in the IWLsWns oi a power plant and con- smokestacl - and Ihjp the particulates ClUflld tnat tms was a sourre of that were analyzed were primarily dlhknia. siliceous, whereas Dow had found ~~ Also. David L. Stalling of the U S. that the dioxins in such emiv-ion* Fish & U uabfe service and asswiates were as.-a mated with cirl>oiiui'e*us analyzed 16 samples of fish and other particulaU aquatic animals for polychlorinated "The particulates we sampled were dibenzofurans and dibenzodioxins. the same as those that come out the They found dibenzo-p-dioxins in only top of the smokestack," Kimble sa>*. The Dow study muJi! .sleeping claims about power plant* being sources of Whs ihe most common isomer in these environmental dioxins based on ex samples, an isomer distribution that tremely limited evidence, she sa>s. would not be expected if the source of What she and Gross have shown is the isomer were ordinary combustion. that at len*t one important class of The most likely explanation. Selling power plants, those that hum western says, is tftat the now njant i rh coal, can he free >f dioxin contami sTJtirPe 'Or tTTi isoiher found in the nation. tTSTT--------------------- ------------------ The question of the need to have HONS 003372 Sep*. 24. 1979C&EN 1? Dioxins, dibsnzofurans can form from burning precursors significantly different from thme ed Control tfrniin Just how important (he trace | quantities of (iinvtns that are being I found in the environment are likely tw I \ be is a point that was raised fro\ precursors present in the material being burned in order to generate chlorinated dioxins or dibanzofurans in combustion has become a central point of dispute. Something, of course, has to provide the atoms that eventually end up in the dioxins and dibenzofurans. Dow contends, based on ita widespread tmdini of tiumuumiif m ummw " "fltrs,' Uno.^ere^Meina to be some middle ground emerging. Crummett, for instance, seems to acknowledge that some materials produce more dioxins when they are burned than do others. He maintains, however, that precursor compounds are so wide spread in tha environment that tracking them down via combustion data ia a task ofsuch complexity and expenaa as to be infeasible. He re ported two new examples of how widespread 2{3,7,8-'rCDD ia in the environment Detectable levels of this compound now have been found in commercial sludge fertilizer made from treated sewage. It also has been detected in the National Bureau of Standards' standard sample of urban particulate matter. Buser and Rappe now say that the synthetic chemical precursors for both dioxins and diobenzofurans can be found ''practically everywhere" in t he environment at low levels. They maintain, however, that, except in special circumstances, such as the combustion of chemical wastes or accidental fires involving stores of they are present in higfter " j^jgtionj^TheycaRB^Ij&^Jt comoustion ol jSSltcmormateomK phenyls {PCB's), which earlier work has shown are very widespread in the environment. Stalling, along with Donald VIT. Kuehl of EPA's Duluth, Minn., re search laboratory, Ralph C. Dow* gherty of Florida State University, certain kinds of chemicals, such combustion presents very little health hazard. And, lika Dow, they think that the use of 2,4,5-T is a very much less important contributor of dioxins and Kappa, finda polychlorinalaii dibenzofurans and naphthalenes hi aquatic animals living in waters that contain PCB's and their breakdown products. The results art somewhat preliminary, since only l( samples to the environment than is combus have been analyzed aod, so far, m tion. samples have been checked fre Even the pristine waters. However, environment from pesticide W MHUUch less hazardous tf ' onujiy twa wu__u_iu lpipone ,. . :Alvin b. Young ofthe r*Air Force's Occupational & En vironmental Health Laboratory, Brooks Air Force Base, Tex. Young and his associates have analyzed the soil and animals at Egiin Air Force combtutmn nmdiM-fa. I Base in Florida where 73,000 kg of Rappppet and Buser have beta I 2,4,5-T was sprayed between 1962 studying the combustion product* at and 1970. Much of this material con chloropnenols, PCB's, and chloffc- tained much higher levels of noted diphenyl ethers and benzene*. | 2,3,7,8-TCDD than .are nosnjound in All of these compounds ton be con the herbicide. ____ verted to polychlorinated dibenzs Some 2,3,7,8-TCDD was , dioxins ana dibenzofurans in baa present in soil samples taken in 1978!" yieiq, tKe^`Tm5!^Howeverr*<3^8 Concentrations ranged from less than TCDD, the most toxic of the ciiom 10 ppt to 1500 ppt. (Young's analyti zodtoxins, is a minor product ol cal method cannot distinguish j rnmhim^inn undar lhe tinmtilioiro 2,3,7,8-TCDD from all other chlori found in municipal incinerator* nated dibenzo-p-dioxins. The con-1 2,3,7,8-tetrachlorodibenzofuian^tb* centration he reports is for the com-j bination of isomers that includes the 2,3,7,8-TCDD isomer.) 1 'the Air Force chemists did not find detectable levels of 2.3.7.8-TCDD in 25%, they find. any plants taken from the site. How Nevertheless, except for^ ever, they did find it in nine species of special cases, they do not s animals, including mammals, birds, dibenzofurans as health hi fish, and reptiles. Levels varied from They do recommend that pq several hundred parts per trillion in rinated phenolic chemical wJ the livers of beach mice and mea very carefully incinerated in ovv dowlarks to 12 ppt in the whole bod that allow for high-temperature ia ies of two kinds of fish. dneration and long residence times to Beach mice, which contained the make sure that toxic pr<iucts an highest concentrations of the com destroyed. And halugenifted phemrib pound, were singled out for further biphenyls, and diphenyl vthew study. Eighteen types ofJtiss^sJtfiOk should not be used as flame retnr qpflqnjmglg wyre examined for toxic dants because of the high tu.xuity o effects, but none of the tissues were their combust iun products. C MONS 003373 Chcmosphere.Vol.12,No.4/5,pp 69-680 1993 Printed in Creat Britain 0045 6535/93/050669- 12103.00/0 193 Pergamon Press Ltd. O . .CE: TV.s MJitoriall be protecr^,, oy /-/ CONTAMINATION OF AN OFFICE BUILDING IN BINGHAMTON. NEW YORK BY PCBS, DIOXINS. FURANS AND BIPHENYLENES AFTER AN ELECTRICAL PANEL AND ELECTRICAL TRANSFORMER INCIDENT. Arnold Schecter, II.0.. M.P.H., Professor and Coordinator, Department of Preventive Medicine, Clinical Campus. Upstate Medical Center, State University of New York at Binghamton, Blnghrmton, New York, 13901, USA; formerly Director, Broome County Health Department, Blngharr.ton, New York INTRODUCTION Binghamton, New York Is located approximately 200 miles north northwest of New York City In Broome County. The city population Is approximately 53,000 persons, the trl city area 154,900, and the county population 1$ about 213,000. On Thursday morning, February 5, 1981, at approximately 5:30 AM a malfunction occurred causing overheating of an electrtcal panel and a nearby electrical transformer within the State of New York's Office building in 3i"ghanton. This overheating led to the release of between 180 to 200 gallons of transformer fluid originally containing 65% PCBs (ArocMor 1254), and 35% tri and tetra chlorinated benzenes. Pyrolytic conversion of these compounds led to the formation of nu-erous furan and dioxin Isomers, which, along with the PCBs con taminated every floor of the office building. Blphenylenes were also produced during this event. Twenty-one months later the building has still not been reoccupied. Clean ing with water and detergent continues as do efforts to set standards for the presence of PCBs, furans, dioxins, and blphenylenes In soot and also in air. It is believed that this.Incident is the first to document formation and contamination of a non Industrial building with these chemicals after an otherwise somewhat prosaic electrical system malfunction. >cause electrical system fires, explosions, overheating with the involvement of PC3s ard In some cases the chlorinated benzenes Is probably relatively common, what has been learned In Binghamton may have general public health relevance elsewhere In both a prospective as well as retrospective fashion. Thursday, February 5, 1982 At S:30 In the noting Binghamton firemen and police responded to a fire alarm at the Binghamton State Office Building (BSOB), a 22 story modern office building, located in downtown Binghamton, which was and Is part of a one block governmental complex. This consists of Binghamton City Hall, the Broome County Office Building, the BSOB and a comm plaza as well as two levels (basement and subbasement) of common parking garage. An electrical panel, one of two In the basement, was found to have overheated. This overheating which created loud noises, like explosions, was estimated to have lasted 5-30 minutes. The nearby transformer, which had originally contained approximately 1,060 gallons of transformer fluid, leaked an estimated 130 to 200 gallons of fluid onto the floor. Dense smoke was present in the area around the transformer. Smoke had been previously vented from the building through two safety doors on the roof at the top of each of two staircases which had opened In response to the smoke or heat. Doors leading to the outside and into the basement level of the narking garage, were opened and large fans used to remove snoke. It was later noted that there were two air shafts beginning In the celling of the area housing the two panels and transformers which vented the men's and women's rears located on each floor and which terminated at the top of the building. Snoke was later found to have passed through these shafts, through metal 669 MONS 003374 TYPICAL ROOM STATE OFFICE BUILDING BINGHAMTON, NEW YORK HONS 003375 671 TYPICAL FLOOR PLAN* STATE OFFICE BUILDING BINGHAMTON, NEW YORK HONS 0033V6 gratlms on the wall of each bathroon .into the bathrooms.and was then distributed in a non homogeneous fashion throughout the usual working areas as well as hidden spaces, including air ducts, elevator shafts, plenums above the ceilings, desk drawers, inside file cabinets, as well as In typewriters and other office equipment. For reasons which are not clear at this time the usual circuit breakers and other safety devices designed to prevent overheating did not prevent the overheating which occurred. The transformer room, as previously mentioned, was not sealed off from the rest of the building, there was probably also a significant pressure and temperature differential which assisted the distribution of chemical contaminants. At the time of the accident the temperature outside was below zero fahrenhelt and the building temp erature in the sixties except for the overheated transformer and electrical panel which was estimated to have been overheated to up to several thousand degrees fahrenhelt. A strong chemical odor was immediately noticed by firemen and policemen a security ?uard and an engineer Involved In the incident. This same odor was also easily noticed n the basement and first floor of the nearby City Hall, including the basement jail area as well as the police headquarters located in the first floor and basement. The fire department In a portion of City Hall also had a chemical odor. Outside of the BSOB a strong odor consistent with the presence of PCBs or polychlorinated benezenes persisted for several days. The firemen and policemen went to Binghamton City Hospital for emergency department valuation of their chemical exposure. Within hours a representative of the General Electric Company, the manufacturer of the damaged transformer. Informed medical personnel of the composition of the transformer fluid. A health emergency was declared and dill personnel except for emergency workers, including fire and police personnel, evacuated the entire governmental complex. This ban on the use of the City and County Buildings continued for a total of 4 days, through the weekend. The State Office building could not be used because of loss of electrical power. The parking garage under the govern mental complex was contaminated with levels of PCBs, as high as 2,000 to 4,000 micro grams per square meter, employing hexane soaked wet wipes on the concrete floor. ' After Us contamination was appreciated, it was closed, steam and detergent cleaned twice, tested for PCBs, dioxins, and furan levels, and then reopened several months later. A command post was set up on the fourth floor of the adjacent City Hall which was ' used for the next few weeks by workers involved In the Incident until the recognition of toxic chemicals lead to the use of a trailer and portable toilets nearer the building end geographically removed from non Involved workers. ; Within days cleanup work began on the BSOB to remove the soot covered material * found throughout the building. Both experts In toxic chemical removal were employed as well as janitorial workers of the State of New York who began washing and vacuuming the building. Electrical system repair was begun during the first week after the Incident. The goal Initially set by the State of Hew York, the owner of the polluted building, was to Open the building within days or, if necessary, weeks. This goal was set on day two of the Incident. This Initial goal assumed that contamination of the air with PCBs and chlorinated benzenes constituted the totality of the chemical contamination. Because of the electrical failure venting of the building to the outside air was not possible. The windows of the building do not open. CHEMICAL ANALYSIS ' Initial chemical sampling and analysis performed by Mr. Charles Gamer, an industrial hygienist on loan from the nearby IBM Corporation factory confirmed the presence of chemicals consistent with those In the transformer in the air of the basement and first floor of City Hall. Later study revealed air ducts running from the 8S0B Into the basement area of the Immediately adjacent City Hall. Air and soot samples collected several days after the incident and analyzed by Gilson Laboratory and separately by Dr. . James Carnahan of the General Electric Company revealed PCBs present within soot as well as air levels as high as 80 mlcrograms per cubic meter within the BSOB and many floors above the transformer several days after the incident. Air levels of PCBs fell to a level of 1-3 mlcrograms per cubic meter, and these levels persisted for over a year when HONS 003377 67 J Photographs of th* Governmental Complex in Binghamton New York, from cop left, clock-lee: The Governmental Complex with the County Building of the left, then the State Office Building* followed by City Nell and the City Council Chamber*. A desk with aoot on it and a window* photographically darkened, in the State Office Building. A worker in the polluted building apparently wearing on asbestos protective mask rather than * NtOSH approved meek protective againat organic vapors and particulate matter. The 'swaged electrical panel (left), the dameged transformer and an apparently undamaged electrical panel. Soot la apparent. A cleanup worker In February, 1981, in the contaminated building, not wearing hia glovea or mask and with an open protective suit exposing his own clothes. HONS 003378 674 measured by standard methods sampling and analyzing PCBs in air. Analysis of soot semples collected in a number of floors In the building revealed levels of Arochlor 1254 as high as 10 to 20% by weight. There was not a readily apparent pattern to the soot or PCS distribution. PCBs were measured In elevated amounts even where no visible soot existed, as In the first floor cafeteria. Sampling of the fourth through seventh floors, and the corresponding stairwells where soot of aflocular nature as well as heavy despositions of soot were found, revealed PCB contamination in all areas initially sampled. These included, floors, walls, light fixtures, ceiling panels, sprayed on insulation and beam within hidden aspects above the false celling (plenums), within file cases and desk drawers, and later, within air ducts and elevator shafts. The area of visibly most obvious soot was In the men's bathrooms especially in the middle floors such as the fourth through seventh floors where soot was noted to have flowed from the air vent areas through the metal grating into the bathrooms and under the bathroom doors Into the general office work areas. According to verbal accounts from Binghamton firemen they did not find this distribution of soot remarkable. Sampling for PCBs from other buildings In downtown Binghamton, revealed levels from 0.1 to 0.7 micrograms per square meter In older buildings to non detectable In some newer buildings employing a dry (filter paper) wipe sampling technique on floors, desks and walls. Within seven days after the incident Or. James Carnahan of the General Electric Company laboratory at Schenectady, New York notified us that furan Isomers were present in the 8506 soot in amounts above what might have existed from trace contamination of the original transformer fluid. This suggested pyrolytic conversion of the PCBs as previously found under laboratory and Industrial conditions. It also raised the possibility of similar pyrolytic conversion of the polychlorinated benzenes to the somewhat more toxic dioxin Isomers. An elequent isomer analysis of a sample of soot was performed by Or. Oavid Stalling of the US Fish and Wildlife Bureau which extended the previous furan findings by providing confirmation of specific furan Isomers and also described the finding of dioxins and biphenylenes. The presence of the dioxins Including the highly toxic 2,3, 7,8 tetra chlorinated dioxin isomer was later described by Or. Patrick O'Keefe and . colleagues at the New York State Health Department as well as by Dr.Christoffer Rappe and Dr* Hans Buser. Each laboratory and each sample led to somewhat different values as would be expected given the non homogeneous nature of the soot and the technical difficulty of the chemical separations and analysis. Later analysis confirmed the differing amount of these various chemicals in various locations within the building. ' later analysis of the concrete parking garage floor after two slow detergent cleanings showed small amounts of total furan and dioxin Isomers at levels as high as 127 nano- * gram total for those isomers measured, with the furans markedly predominating. An ! adjacent building's parking garage, also less than 12 years old, had essentially non 1 detectable levels of furans and dioxins present; hexane or benzene extraction type wipe technique was employed In the latter Instances in order to extract a higher percent of the total amount of chemicals present, usually we found from 1:1 to 10:7 ratios of PCBs on adjacent sections of contaminated floor or concrete by " wet" (solvent wiping or dry wipe technique, respectively.Analysis performed by Prof. James Spalik of B.C.C. A representative finding among the Initial chemical analysis is that of Christoffer Nappe and Hans Buser which showed: PCOO Total level 2,3.7.8-Tetra-COO 4 other Isomers (1.3,7.8-, 1,4,7,B-, 1,2,3,7- or 1.2.3.8- and 1.2,7,8- 1,4,6,9-) Total level tetra-CODs 1.2..3 JJ^Penta-COP 7 other penta-COQ isomers 20 0.6 ppm PPrc 0.6 ppm 1.2 2.5 . BP* 2.5 PP" HONS 003379 1,2,3.4.6,8- + 1,2,4,6,7,9-Hexa-CDD 1,2,3,6,8,9-Hexa-COD 1,2,3,4,7,8-Hexa-COD 1.2.3.6.7.8-He*a-CDD T.2.3.7.8.9-Hexa-CDO 1,2.3,4,6,7-Hexa-CDD Total level hexa-CDOs 1,2,3.4,6,7.9-Hepta-COO 1,2,3,4,6,7,8-Hepta-C0D Total level hepta-CDOs Octa-CQQ PCDFs 2t3,7,8-Tetra-CDF Total level 1,3,7,9-Tetra-COF 6 other t:etra-CDF isomers Total level of tetra-COFs 1,3,4,7,8-Penta-CDF 1,2,4,7,8-Penta-CDF 1,2,4,7,9-Penta-CDF l,2r3,7f8-Penta-CDF 1,2,3,6,7-PenU-COF 1,2,6,7,8-Penta-cpF 2.3,4.7.8-Fenta-CDF 2,3,4,6,7-Penta-COF 12 other penta-CDF Isomers Total level penta-CDFs 1,2,3,4,6,8-Hexa-CDF 1,3,4,6,7,8-Hexa-COF 1.2,4,6.7.8-Hexa-CDF 1,2,3,4,7,8-Hexa-COF Total level hexa-COF 675 1.2 ppm 1.3 ppm 0.7 ppm 0.6 PP" 0.4 --Bm 0.5 ......PP" 4.7 4 ppm 3 PPm 7 2 PPm 2160 12 1 15 28 ppm . PP ppm --EE"! 65 ppm 25 ppm 22 ppm 310 --2E5 60 ppm 25 Ppm 48 ppm 12 ppm no ppm 670 Ppm 30 ppm 125 ppm 50 ppm 310 PP* 515 ..m. MQNS 003380 676 Patrick O'Keefe & Smith New York State Health Department, 1981 2.3.7.8 TCDO & 2.3,7,8 TCDF Transformer Soot - Blnghamtoa-State Office Bulldtn? Analyltlcal Result (ppm) Sample TCDO(1* Binghamton soot #1 3 TCOF1 273 Binghamton soot #2 4 124 Average Value 3.5 200 Both samples were composite soot taken from floors 3 & 4 (1) 2,3,7,9 TCDO - Tetrachlorodibenzo paradioxln 1 (2) 2,3,7,8 TCDF - Tetrachlorodibenzo furan David Stalling, Ph.O., United States Fish and Wildlife Bureau, 1981 Binghamton State Office Building Soot TCDO 5 ppm 2378 Tetra CDO TCDOS Tetra - CDFs 5.4 pp Penta - CDFs 105 ppm Hexa - CDFs 512 ppm Hepta - CDFs 101 ppm Octa - CDFs 30 ppm Total Furans 753.4 ppm Blphenylenes 50 ppm WRIGHT STATE UNIVERSITY. BREW LABORATORY. DAYTON. OHIO 45435 RESULTS OF HRGCAlWS AlMLVSIS OF UfPE SAMPLE <iM0Me COUNTY HO. 41 FOR TETRA- --------- TB5abEOrnCTNLogiTiATEC~?rabbot-p-crexrte m preenzoruftAir------------ Government Complex Parking Garage (After Cleaning) Or. Thomas Tieman, 1982 CDD/CDF TEcdd PCDO HxCOO HpCOO Apparent Isomers N.O. 3701^-2,3,7,8 N.D. N.D. 1,2,3,4,6,7,8 1,2,3,4,6,7,9 Total 37C14- 1.2.3.4,6,7,8 Quantity of CDD/CDF Detedted (no/wlpe) N.O. Mlnlmua Detectable Quantity Recovery of (nq per isomer) Internal stds 0.10 .... 100 N.D. N.O. 0-65 0.45 1.1 .... 0.10 0.20 0.20 0.20 0.20 .... 100 HONS 003361 877 CDQ/CDF QCDD Aooarent Isomers 1,2,3,4,6,7,8.9 37C18OOCDO TCDF PCOF HxCOF ` HpCOF OCDF 1.2,4,8 2,3,6,8 2,3,7,8 Other Isomers (8) Total 1,2,4,7,8 Other isomers (13) Total 1,2,4,6,7.9 Other isomers (12) Total 1,2,3,4,6,8,9 Other Isomers (4) Total 1,2,3,4,6.7.8,9 Quantity of 1.0 .... 2.0 3.1 9.6 3S.8 50.4 5.2 11.8 17.0 1.6 43.6 45.2 2.7 4.6 2_3 7.3 Minimum Oetectable fjti^lsaner) inters!. 0.20 ----- 100 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.20 0.20 0.20 0.20 0.20 Q-ZO-- . 0.20 MEDICAL ASPECTS OF THE INCIDENT Toxic chemicals Including those found In the Binghamton electrical panel transformer Incident have been Implicated In an Increasing variety of medical disorders especially In a variety of annual species. These Include skin lesions, cancers, adverse reproduc tive outcomes* central and peripheral nervous system as well as gastrointestinal disor ders, Immunologic deficiencies, and other pathologic conditions. Initially, sane of those exposed to the Binghamton chemical complex complained of skin rashes, headaches. Irritability, anxiety, difficulty sleeping, sexual difficulties, and tingling of the extremities. A collaborative medical surveillance was established which accepted all persons exposed or who thought they were exposed to the toxic chemicals involved. The results of this activity, which includes about 500 persons, are still far from complete at this time. Evaluation included a medical history and physical examination, hematologic tests of blood, blood chemistries for 22 substances including liver enzymes and triglyceride and cholesterol levels from fasting patients. Urine was sometimes taken. Blood PCB tests were ordered but are not yet completely analyzed and available. Special fat analysis for PCBs, furans and dioxin isomers wes performed. Lymphocyte function studies and urine porphorin analysis was performed on one petlent. Elevated liver enzymes and triglyceride and cholesterol levels were found in some of the 500 patients without etiology being well characterized. The percent of abnormal laboratory examinations may or may not be above that expected from a matched control population. Estimates of exposure to the chemicals In question proved a problem. Ideally, serum PCB, furan and dioxin levels as well as cytochrome P 450 5 446, liver enzymes, cholesterol triglycerides, liver levels before and Immediately after exposure might have proved helpful but were not available. Workers In the building after the Initial cleanup effort do In fact have preentry as well as exit medical evaluations Including blood PCB levels. As would be expected from such a large group of persons exposed In this incident a number of medical conditions have arisen, as diverse as malignant melanoma of the skin and transient erythema of the face to fetal damage and wastage where the husband was the exposed partner, to serious psychiatric disorders including an obsession with the exposure to these toxic chemicals followed by a suicide attempt with the patient still comatose months after the attempt. Establishing etiology regarding causation of any of HUNS 003382 678 these medics] abnormalities with respect to the toxic chemicals remains as elusive at the present time as establishing exposure levels of individual patients. It is not the purpose of this paper to review medical aspects of the diagnostic pathologic, and possible treatment options which confront physicians or health officials faced with problems of patients who may have been exposed to toxic chemicals in combinat ions produced by electrical system incidents such as the one documented in this paper. Likewise, I will not review the various animal toxicologic tests, including rabbit skin, guinea pig 10 50, electron microscopic examinations of guinea pig liver tissue, chick embryo tests and others performed or under way at this time In an. attempt to characterize the toxicity of the Binghamton soot. It is Important to note that the soot has not in activated these chemicals as shown by chick embryo fetotoxicity and teratogenicity dem onstrated in pilot tests with the Binghamton soot but not with fireplace soot or activated charcoal as welt as guinea pig LD 50 testing. At the present time over one billion dollars in law suits or the intention to file law suits have been filed primarily against the State of hew York as the owner of the polluted building. Under New York State Law it is necessary to file an "Intention to Sue" within a given time frame In order not to lose the right at some future date to sue the State of New York for damages recognized at a later date. Such damage derived from n Incident might include cancer or other conditions not apparent Initially. Damages awarded under the American judicial system might take into account punitive as well as compensatory damages, and Include loss of Income, medical costs, and other items. In eddition the question of jurisdiction arises. Usually a city or county would declare a potential health hazard through its health department, acting partly under legal powers granted by State Government. The Federal Government has standing In certain Instances, through the Environmental Protection Agency (E.P.A.), the Occupational Sefety and Health Administration (OSHA) or the National Institute on Occupational Safety and Health (NIOSH) as well as other agencies on certain occasions. Here tha State of New York found Itself the inadvertent owner of a polluted building. Instead of Its customary role In acting as a regulator, the State found itself in the role of pollutor. Questions defining which agency regulates a given governmental agency which becomes a pollutor is an aspect of law and public policy which has not been previously addressed to the best of our knowledge in circumstances similar to the Binghamton Incident. It Is however, worthy of note that in the United States at this time a Federal Agency such as the CPA will not enter such disasters without the approval of the State authorities. Because of this entry of the E.P.A. was delayed several months until their aid was sought and obtained by the senior Senator from the State of New York, Senator Patrick Moynihan. CONCLUSIONS and DISCUSSION 1 At this early time less than two years after the Binghamton (State Office Building) incident there are some tentative conclusions which may be made: 1. electrical incidents Involving PCB and polychlorinated benzene containing transform ers, eapacltators. ballasts etc. constitute a previously unrecognized health hazard by exposing persons in non industrial sites including offices and schools to such toxic chemicals as PCI's, furens, dioxins, biphenylenes, and other related compounds. Several simitar incidents including a Binghamton City Kail capacitor Incident producing air 1 avals of 80 micrograms per cubic meter were noted in Binghamton during the year after the incident. ---- ' 2. The presence of these chemicals has not been previously documented in similar cir cumstances so that long term exposure to small or other than snail amounts of a combinat ion of toxic chemicals of this kind has probably been occurring in Industrial countries Since 1929 when widespread use of PCB's began. These Incidents may be contributing to environmentally Induced or promoted cancers, reproductive abnormalities, immunologic deficiency, and possibly premature death from infection, neurologic and gastrointestinal system pathology and possibly, by elevating serum triglyceride and cholesterol levels, excess or avoidable cardiovascular and cerebrovascular pathology. 3. Prevention of some of these Incidents is relatively easily and econorically achieved by redesigning and enclosing PCB containlnn transformers and other PCB containing elect- MGNS 003363 rical systems. Many transformers are already In contained areas. Others, like the Binghamton transformer, are placed in a fashion which easily may lead to significant contamination of the building. Future buildings must be constructed with this newly described potential health hazard in mind and preexisting buildings must be evaluated carefully and, if necessary, appropriate safety features added. Improved circuit breakers or fuses are certainly desirable. Adequate fire safety and temperature dec reasing devices can be Installed to prevent incidents similar to the Binghamton incident. 4. Removal and replacement of PCB and polychlorinated benzene containing transformers, capacitors, ballasts, etc. must clearly be considered If health risks warrant such measures. Refining transformers as with silicon ray diminish the risk. "Dry" trans formers, with no fluid, may offer improved safety, at least with respect to toxic chemical exposure. Mineral oil containing transformers, while posino a fire hazard, appear to be less of a toxic chemical threat. 5. There is no unanimity regarding standards for PCB's in gaseous phase even in Industry at this time. The current United States OSHA standard for PCB's in air for Industry Is 5C0 or 1000 mlcrograms per cubic meter, depending on the isomer mix. However e National Institute on Occupational Safety and Health (NtOSH) Criteria Docu ment has taken the position, that no exposure to PCB's should be considered safe or desirable. To implement that point of view it was suoqested in that document that one mlcrogram per cubic meter, the minimum level of detection at that time, be used as a value to replace the 500 or 1000 micrograms per cubic meter standard. Different values may well have to be established for younq children, pregnant women, and other special cases to adeguately satisfy conditions as demanding as those found in Binqhamton and doubtlessly elsewhere, simply awaiting confirmatory chemical analysis. Standards for PCB's In soot, or for dioxins, furans and blphenylenes in soot or air need to be estab1 ished. 6. National and international levels for those chemicals must be established not only for buildings ami various portions of these buildings, such elevator shafts, air ducts, and elsewhere, but also for human body fluids and organs. At present, serum and fat deteminatlons of PCB, dioxin, and furan Isomer levels are fn early stages of being used to attempt to document levels of exposure. Individual Isomer analysis of body tissues may prove useful. As clinicians we have values to consider for lead, arsenic and other chemicals in body fluids, but we do not currently have clinically meaningful Values for dioxins, furans, biphenylenes or PCB's. Determination of metabolic pathways and usefulness of blood, fat, urine or fecal levels of these compounds and their metabolItles will doubtlessly lead to data useful to clinicians evaluating and treating patients after related incidents. 7. Because toxic chemical exposure Is a rapidly increasing health problem, it may be appropriate that serum be drawn and stored for all willinq members of the population at several points in time In order that comparisons be made when Indicated to be able to evaluate level of exposure after an individual Incident. At the very least, none eleva ted but low levels of a given chemical found after chemical contamination might prove quite reassurino to a patient. In the Binghamton Incident persons without previous blood samples available were exposed to various amounts of PCB's. dioxins, furans, Mphenylenes and other pyrolytic byproducts. Because of this, blood PCB and furan and dioxin analysis will be very difficult*to Interpret. Fish from the Hudson River In Hew York are frequent ly high in PCB levels and fish from the Great Lakes have been found to contain significant levels (In parts per trillion, P.P.T.) of dioxins, including 2,3,7,8 TCD0. Previous exposure to Industrial chemicals or herbicides containing dioxins, PCB's or fur provides further confounding variables. Ulth a presumed relatively low level exposure for most of the original 500 persons under medical surveillance it will be difficult to differentiate origin of postlve but low levels of PCB's found in body tissues. Isomer analysis and fat biopsy data may be of value but these techniques are still experimental and the amounts present,expecially since some samples were taken long after the incident, may be too low to detect accurately at this time. Frozen samples for future analysis may prove useful. 8. Medical surveillance of exposed populations following similar Instances from both an occupational medicine standpoint as well as an epidemlologically oriented study is desir able. For the individual patient and his or her physician knowing what to look for, and when, and possibly being able to decrease body burden of these toxic chemicals if present HONS 003384 in elevated levels by pharmacological or other means is certainly medically desirable. Although epidemiology provides only a weak tool for dealing with relatively small numbers of persons or subtle events, It certainly may be of some usefulness in events such as this one. Certainly, as better physiological indices of exposure become avail able, whether urinary porphyrin patterns, fat, biood, urine or fecal chemical analysis for the chemicals, cytochrome P450 or P448 alterations, electron microscopic lesions of hepatic parenchymal cells characteristic or pathognomonic of toxic chemical exposure, patterns of elevated liver enzymes or increased serum cholesterol or triglycerides, en hance the usefulness of large scale collaborative studies and reoistries will come to be of markedly enhanced value. At present, relatively small numbers of patients as well as Imprtclsa estimates of exposure constitute major problems in human studies. 9. Intense multispecialty research into all aspects of such accidents is needed. Psychiatric research to understand and prevent psychiatric illness following these en vironmental incidents is especially needed. Medical research considering how patients exposed should best be monitored and eventually treated Is urgently indicated. Further research to explain why chemicals which seem so toxic in numerous aninal species have not been demonstrated to be as toxic in man is essential to differentiate between species differences which might show man relatively Impervious to these chemicals or simply to establish better studies demonstrating toxicity in humans. Better, faster, cheeper, readily performed sampling and chemical analysis techniques are certainly needed. Oioxln and furan isomer analysis frequently cost SI,000 to S2,0Q0 each and take months to complete. These are far too costly for most parties involved and almost no organization is willing to shut down entirely for months waiting to learn wnetner or not a potential health hazard exists. Legal and legislative research is needed in-order to consider whether the current adversarial and legal approach to redressing wrongs and hopefully obtaining justice through law suits, now epidemic in the United States, is the most reasonable aoproach to justice for those 'njured by incidents of toxic chemical contamination, leoislative alternatives to the judicial process are possible, such as workman's compensation, or specialized approaches similar to the black lung coal mining legislative approach which supposes that working in a mine for a given number of years followed by lung diseases of certain kinds are compensable without involving a court of law are also possible. In Australia, Veterans of the Vietnam War who become ill in a fashion which miqht be attibu- ted to toxic chemical exposure are compensated unless the government can prove that the Illness was not caused by Agent Orange containing 2,3,7.8, TCDO. Each of these financial and legal approaches has advantages and disadvantages, but the toxicity of these chemicals in man may remain subject to viqorous research and disagree ment for many years. While scientists continue the tedious and necessary research to / Its ultimate but slow course justice will be souoht in one way or another by those r exposed to toxic chemicals at great cost to all involved. 1 10. Interdisciplinary communication with scientific colleagues and the oeneral public with frequency as well as maximum clarity is essential. Meetings such as The International Dioxin Conferences with promptly published proceedings, and with naximun participation of numerous views is desirable. Hopefully future meetings will also have scientific present ations from colleagues In sociology, psychology, law, anthropology, political science and case studies from physicians and from affected persons themselves in order that wt may coamtunlcate most effectively in an interdisciplinary fashion and learn from one another. Possibly even panel sessions including responsible and knowledgeable members of the press would contribute to Increased understanding and better communication between those tnvolved In pest and future incidents involving these toxic chemicals. HONS 003385 c* /5-T-/7Y /J FORMATION Of POLYCHLORINATED DIBENZOFUHArr., (PlDFs) THE PYROLYSIS OF INUi.lDUAL PCB IbCMERS Hans Rudolf Bu.r Swiss Federal Research Station CH - 8820 Wadenswil, '*itzerland and Cnristoffer Rappe Department of Ott.inic Cht-mistr/, iJnivcr-.it/ of lime? S - 901 d7 'Jmef, " eden introduction the polychlorinated dibenjofurans (PcDFs, structure -.eo belowi are a senes of tricyclic aromatic compounds, in chemical, biological and 'oncological respects nrc/ similar to the polychlorinated diben/o-p-dioiins (PCOCs, see belowi ' In all, there is a total of US different positional PCDF isomers, namely 4 mono*, 16 dt-, 28 tri*. 38 tetri-. 28 penta-, I6"hea-, 4 hepta- and 1 octa*C0F. The most toxic isomers appear to be the 2,3.7.8-tetra-, 1,2.3,7.8- and 2,3,4,7,3-penta-COF, which all can be compared to the extremely toxic 2,3,7,H-tetra-CQO,*' and which all "iv ***?* ! /i*d 'r, tne Yusho poisoninq.-1 ,S 1ST HONS 003386 Lr?F5 have been identified is undesired trace contaminants in chl-'r Jerivatives like phenoxy i'.:js^ and in ;>olychlornated Dijin n-. ' ,, ntlv, rCims have been in n -1 ,jd flue gases of nuniri M ,,'i icesses. PCBs are industrial cheroica's of wide use and they are now vr0wn to to . 1 . distributed m the environment. Although r*ie thermal conversion of PCBs into PCOFs under jy'olytic t.ondi Mn's '.ould se e-peci*', experimental evidence to our know1 reported p*ior to our previous papers. ^ 1 ci,, PCBs AT Cl, Cly PCDFS uyin*n However, increased levels of PlDFs vpim-rangel *pre observed m i PCB heated to 300 for I week in the presence of lir, arw in a PCP used in a heat e<chanoe system for extended 14 15 periods of time. ' In our previous papers we have reported on the formation ot PQFs from the pyrolysis sealed quart* mini-ampoules in the presence of air at temperatures of 500-700 C. The yields of tho HCOFs were in the range. In addition to PCDfs, unreacted PCBs, chlorinated benzenes, naphthalenes and other chlorine?' l vonpounds were il'o v.orvcd; polychlorinated hydroxybiphenyls were found as possible intermediate products By using high-resolut ion GC and MS. have further >hown m.i* lost e t'H- Majur PCDF isomers found in two fly ash samples were the same as those f..r-wM n ,r.i/sis of the most conmon commercial PCBs, giving strong support `hjt th.--,f* P';r, r:-tn,p from the uncontrolled burning of PCBs. Using individual PC'S i sorer-.. w i. : -"i the cyclization processes in the,*.- pyrolyses are mtra.-nolvujl i* jr.t wv hi..- rut the following three reaction routes leadirg to different PCPF punier* f.--~n KB: 10 \*v nittion route I: 'toss of ortno-CI,) MONS 003387 reac ion route 2: (loss of HC1 involving a <?, 3-chlorine sh i f t) ci. Cl Cl H -HC! react_i_on rout? 3: (loss of ort^'-HC |) Cl, Cl H Cly - HCI Cly In tms paper now the occur'* of them reaction **-njin *ne oyroly.- '* individual PCBs is further doc j-.- j \d. fhe turnation ;{ m:;>Fs was nvesti - itM :n pyrolysis *periments u-> m> ; ' ,i - , ' ' 'v.i-, . senj- >* 1 i octj nloru* biphenyl. Our experiment-. -w il i * / ,, ` in,. \tov<- r,n.t > o. ,, ,md *'*05e cjp bo used to predict the formation of .i-ucific PCOFs. four'h, additional teaccion route was found to occur with r,,re .' reaction route 4: {loss of ortho-H^) Cly t uvr ! Polychlorinated bipnenylsoused for ,,roiy>;-> Eighteen PCS isomers were obtained from . inous v>i,r < i . r !. isomers were checked for isomeric purity and absence of P*..fs um"i . '*'> .. : described. Single peaks were obtained and Purify wa> found to .':o ;evrill, of the PCBs contained detectable Quantities of PiCr*\ . 1 . : , were prepared at concentrations of MJ m,>il in hpnjene. Micropyrolysis of PCBs Individual PCB isomers (IC0*g each) were pyrolyjed at o;lUf in separate ;.art: in : lnpon l?S . The "'l.' pyrol/SiS rondiMons were as previously Vr>**iDed. 1 ,.-f '''-..''Tie was idded to each ampoule. A c-yl ,il; ,uct was usee dm^tly HONS 003388 Table 1. List and sources of PC3 isomers investigat'd Compound Source Compound ,"urce 2,3,4,5-tetrai.hlorobiphenyl 2.3,5,62,6,2',6'* a a b 2,3,4,5,6-pentacMorobioheny l 2,4.6.2'.V2,4 , !>, 3' ,4*2,4.6,2' ,4'- c c d c a 2,4,5,2',4'.5'-he' 'chlorobiphenyl 2,4,6.2` ,4' ,b ` 2,4,5,2 ' ,4 ' ,6' 2,3.4,2' J' ,4'2,3,5.2',3', S'2,3,6,2' ,3 ' ,6' 3,4,5.3',4' .S' 2,3,4,3,2'.3',4'-heptacnlornb*phenyl 2.3,4,5,2' .4',5'- 2.3.4,5.2' ,3',4' .5*-octachlorobipheny1 b h V. I 1 a > e e c ,1 * Dr. J. McKinney, National Institute of Envi ronmental Health r-'. iences. Research Triangle Park, NC, USA b * Dr. K. Andersson, University of UmeS, UmeS, Sweden C * RfR Corp.f Hope, RI, USA, courtesy nf Dr. J. McKinney d 1 Or. C.A. Wachtmeister. University of Stockholm, Stooholm. Cw**den e * Or. V. Ma suda, Oaiichi College of Pharmaceutical S`. , 5i,uo>>j, Japan 6C-MS Analysis A Fmnigan 4000 quadrupole GC-MS instrument with El source and coupled to a SO m 0.36 m 10 QV-17 glass capillary column was used. Ihe column was interfaced to the MS vja a platinum capillary interrace. The operating conditions were as previously described,'^ however, the column show* i somewhat higher elution temperatures for PCDFs (".amt order of elution) than a previous OV-17 column interfaced via a glass l<n*d stain less steel tube. In a first phase, complete mass spectra were recorded using the data system. In * second phase, the samples were reanalyzed with optimal uwht separation usn; *mss specific detection (mass fragmtntography) of PCUfs by nor.'* T in-) ~olec 11 >r ; r-, .r * .. 270, 304, 338, 372, 406 and 440 for the tri- tO OCtacl'Inro c ompr>,yn,J5 . Standard and reference PCDF isomers The PCDf isomers available as reference and standard < or.puunds for ,.r. ,, investigation art listed in Table 2. They were the gifts of Crs. Mjsiidj. ^ *im,y. Morita and Roland, and of Mr. Gar) and Mr. Lindahl. In FTgure I, we give ras . *rj, .>nto- grams of a composite sample of these compounds showing the elution of tetra-. aid heia-COfs (peak Identifications given in Tatle 2). In addUion.we established the elution order of the 4 h*pta-CDFs (i.ZJ.i.e.i.n* * 1,2,3,4,6,7,9- 1,2,3,4,6,8,9- 1.2,3,4,7.8,9- ; all separated on Ov-17. see Figure 5) from chlorination experiments (SbCI^ in CC14, \e> min at 50C) using ?,3,7,8* *n r-a-, l ,3,4,7,9-penta- and l ,2,4,6,R,9-he*a-CDF, 1 ,2,3,4,*>,7,/*hepta-iOF was present .1 minor product m 2,1,4,6,7,8-hexa-C0f. HONS 003309 Table 2. Standard and reference PCDFs used in the present study Compound Peak number (* fig. 1) Source and remarks 1,3.6,-tetra*C0F 1.3.7./2,4,6.a1.3.6,71,7.4.62,3.6,a7,3./.8* 3.4,6,?- 1,7.4,6.8-penta-CDF 1.3.4./.a1.2,4,7.81,3,4,7,91.2.3,7,8- 2,3,,6,81,?,3,4.81,7,3,6,72,3,4,8,92,3,.,7,81,3.4,8,92.3.4,6,71.2.4,8.9- 1,2,3,4,6,8-hexa-CDF 1,2.4,6.7.81,2,4,6,8,91,2,3,4.7,81,2,3.6.7,8* 2,3.4,6,7,8- l,2.3,4,6,7,8-hepta-COF - 1 2 3 4 5 6 7 8 9 10 n )2 13 14 IS 16 17 lfl 19 7) 71 :7 23 74 25 76 77 - a a ,b 0 b.c a a a ,d e a c.f b (contains also 1,3 ,4,9-j Lnta--.Cr 1 d.b (contains also 1,2,4,H,9-pentJ-lDF) b 9 c.f f d i e b (contain* also 1,3,a.7,3-penta-CDF) d b (contains also 1,7,4,7,a-penta-COf) c.f c.f c d d c.f (contains also 1 ,2 .3 ,-l ,6 .7,3-neota-lOF 1 C.f (contains alio i , 3.4 ,b . 7 ,d-nMa*COF a t Or. H. Morita, Tokyo Metropoltan Research laboratory of Pub! Ja:- b * Hr. R. Lindahl, University of Umea, Sweden; prepared through Pj !! a^nte cycluation of polychlorinated diphenylether.16 c * Hr. A. Garl, University of Ume5. Sweden; prepared from acetylation, chlorination and reduction.1' or.---. ,% d Or. Y. Hasuda, Daiichi College of Pharmaceutical Sciences, F<juom. Jiwn e Or. J. HcKinnty, National Institute of Environmental Health Sciences, St-sear,, n Triangle Park, NC, USA f * Hr. A. Garl. University of Umel, Sweden; prepared through Pd/.[ii< itc c/d'.Mt^ of polychlorinated dtphenylether.^ g Or. A. Poland, McArdlt laboratory. Madison. Wise., USA HONS 003390 15 "" hxa- "1 " 290 1 1 ~~ 1 230 r-------------1--------- '--"------------r-------------210 C --4*- - penta- --"-- tetra-CDFs Figure 1 : Mass fragmentograms ** 304, m and 1/2) of a composite samole of different FCDF ref*ri ce compounds so-minn l*jtion of f>r and he*a-CDFs 'for p ik identt f il.Um ' , .* ' iP 1 * '; ; u 'i glass capillary column, _ " hm-i. !. - )G * -in I t.f, .ini ;;i \ < ?%ro lysis of tetrach 1 orob i r,*,ny 1 The pyrolysis of three tetracnlorcbiphrevl, < , . :> i '! ' "i . fragmentogram* of the pyrolyzed samples ir- qw*i m f : ;ur.. , !</ '*0* .t trt- and tetra-COFs. The pyrolysis of 7 ,3,<1 ,S-tetracnlornhipunny 1 load m.. * c 1 c tetra-CDF (see Figure i'ai. The former is expected to n* . .3,tri-luF romeo *:.j reaction route 3 (see Scheme below). The formation of j tptra-fDF from this pi;9 has involve a new, prevtOu'ily^ not. observed reaction rnuv wit" loss >* ortho-" , '"u.'i to routed. Scheme below); 'he ; some r e pec tod 1; 1 1-'<*tr i-i :.f . The ,u >* -i IF .is ilso h fro-r? yyrol/sr. of /, 3,4,h-:'nt. h 1 >(;:;,neoyI see T.at.. i - .!* I 'r * r *.,* f * .xn 1*r* rjcn I rrnb n,,`i,r /1 v'.i ri*.ttior rn>.'.., 1 n1 MONS 003391 i'\J in fact only very minor ^mounts of additional isone-'. **re observed. .-..jtin in . \i. 'Ot.- formation 0 f t tri-crr. ! / iof > tc I , .j i ! !l-jJ Mt? I ..!, * - * r i f "r r r*nr..t i i '< < 3. The formation of It-. r I Vt.)- f: P ; from tm, I'UJ vit r.n.ti.n r. j-.c, . 4 is not possible and in fact no nid i t \ 'hi.i I PCiTs *ern ol'servtd. Figure l : fragmentograms tm/e J70 and 304- of pyrol/Md t*tracnloroDont`nyls ,'i''wtno rlutton of tri .tnl tr tr a -1 IT s'* from fa' . ,3,4,^*, {0) ?,3.*.t>- ! 1 i " ,f>1 - f et ra. h 1 orobi phen> '. conditions as to Ft ;yre ) .* ' "Mi. 'i i-e -it ve m parent lies r.. HONS 003392 d: and a tri-CDF (elution of tri-COF shown in Figure c 1. The expr'-d di*CDF is the 1,9- substituted isomer formed via reaction route 1. The formation of a tn-CDF from this tetracMorobiphenyl has to involve a rearrangenenr n ' n. the isomer p*3*ctpd is l,4,9-tri-CDF (reaction route 2). TMs PCB cannut form tn - and tetra-CDFs vu re.> tiw routes 3 and 4, and again no additional iCDFs <>b;ervf?d. Cl Cl Pyro 1ysls of pentachlorobipheny1s The pyrolysis of five pen techlorobiphenyls was investigated isee Table I). Mass fragmentograms showing the elution of tri-, tetra- and p?nta*CDFs are given in Figure 3. The pyrolysis of 2,3,4,5,6-pentachlorobiphenyl lead to the formation of a tetra-COF as the major product and smaller amount of four tri-CDrs (see Figure la). The tetra-COF expected is the 1,2,3.4-subStituted isomer formed Via r.-xfion route 1; the -Mime isomer was also observed from the pyrolysis of 2,3,4.-j-ietrachlorobipneny 1 The formation of PCOFs via reaction routes 1, 2 and 4 is not possible from this PCi3 f .-ding of small amounts of tri-CDFs could mean that these PCDFs are foi.ned m i i f ic df'ilor- ination process of 1,2,3.4-tetra-COF or of penUchlorobipn-nyl -rvu- ,, i . tion. In either case, the expected PCOFs contain C!-substituents e'tiusiv'i, m .p > m* r*,, carbon rings of the dibenzofuran nucleus (4 possible * *h.. -r. ;r., *ern tentatively identified as 1*2,4- and 2,3,4-tri-C0Fs, pyrolysis product', nt .'.i.i.-- jnd 2,3,5,6-tetrachlorobiphenyl (set Figure 2a and b). As show* in Figure 3b, 2,4,5,2' ,5'-pentachlorobiphenyl formed a major tn-uif u 1 smeller amounts of 4 tetra-COFs and a penta-CDF. This number of rcoF* be * pec ted from the pyrolysis of this PCB via reaction routes I, ?, 3 and 4 (see Scheme below). PCOFs identified by co-chromatography with reference compounds (see Table 2) were 2,3*8- tri- and 2,3*6,8-tetra-COF formed via reaction routes 1 md ?, respectively. So far, no attempts have been made to assign the remaining tetra-COFs. A small amount of a penta-CDF was observed; the expected compound is 1,3,4.6,9-penta-COF formed via reaction HONS 003393 ci ci ci ci The pyrolysis of 2,4,5,3',4'-penidchlorobiphenyl lead to the `creation of two tetra* and a penta-CDF (see Figure 3c). No tri-CDFs cjn be expected frori *n>s ?>:a via reaction rout* 1. The two tetra-CDFs were identified by c^-chromatography witn reference compounds (see Table 2) as the 2,3,7,8- an: \1,6,7- substituted isomers, for-ned via reaction route 3. ih.s PCO cannot form tetra-CDFs via reart m roijie t' ini n fur additional tetra-CDFs were observed. Pyrolysis of this PCS is e-oectrd forn penta-COFs via reaction route 4, namely 1, i .4,7,.i- md 1 , i.4/ . f 3^r^e below). However, only the formation of 1.3,1 .i-CW < : 1,3.4.78- (: 34,87-) HONS 003394 Maso fid*; tit j penU-CLf * ? bi pneny l. . j : i' . . . -. : . > i .. pyrol/Ji-d pentach I oroL < pfit' , s i.bwin-j uljtn of i-, -Lrj- jiw .V -, 1*. 1 ,4 ,v . i` ,4' -. '1) . ,4,v ` .4'- ar o . 2,, ,.;i.tocn o HONS 003395 Pyrolysis of 2,4,6,2' ,4'-pentachlorobfphenyl gave a fr-*-jnn "r"*' *(?!* i, snown ! Figure 3d. This number of isomers con be routes I. 2 and 3 (see Scheme below). Hie Dn:,i.l.in nt ,j -*om . > r>-1 1,* ,vi,' , . . not possible and in fact no penta-C.Or ,,ss . 1,3,7- substituted isomer. Two of the tetro-CDFs were tnn'n.ned as IJ.fc,.'- r.g i ,;. t tetra-c_<F :ormed . >_a reaction routes 4 ij >, . , eluting) i; expected to bo 1 .3, t , 7-tPtrj-CPF , *-'l1 i o"i 1 )snr"f*- i rnuN> ?. Cl Cl Cl Tin , , rol /, i s of , 3 ,`j , " ,i. 1, . and five tetra-CL'Ts (see Figure 3v. v, .........,'.,j ind J Set- $cln#m# below), A'tam, t , not possible ana in fact no .,-c; i * : ( 14,6,8-) (12,68-) U48 (1,26,9-) (1,4,69-) HONS 003396 One of tut main products was tentatively identified as 1,2,4,8-tetra-CDF. p ./duct of 2,4,5,4'-tetrachlorodiphenylecher. 18 Two of the tetra- , ,ruiysis >d 1,4,6,9-) are also expected pyrolysis product: of 2.3.6.?' J' .5'-npxa. hi rj5'.u.n/i ;sre later). Pv o1vjis of hexachlorobiphenyls The pyrolysis of seven hexachlorobipheoyls was investigated (see Table I). Mass fragmentoarams f ?vrol/*ed samples a'-? gn^n in figure 4. They shew i tetra-, pvota- and hexa-CDFs. The results of the pyrolysis of 2,4,5,2" ,4',5'- and 2 ,4,6,2',4',6 -hexachloro- hiphenyl were previously reported. However, tn,- identity of son* of the resulting >;COFs was tentative and could not be con' .....>d at tnv f~>r 1 xch of referemv compounds. Additional standards available now made poss'ble to confine >h*se tentative identifications. In case r. 2 ,4,5,2' ,4' ,u'-hexachlorobipheny 1, tne tormanon of a tetra- and two penta-CDFs was observed (see figure 4a). These PCDFs were identified js 2,3,7,8-tetra-, 2,3,4,7,3- j"d l , 3,4,7,8-penta-uJF formed via reaction routes 1, 2 and 3, espectively. [n rase of 2 ,4,5,2' ,4' ,6 exachlorobiphenyl, a tetra- and a penta- CDF were found (See Figure 4b' mj identified as 1,3,7,9-tetra- ind 1,3.4,7 ,9-penta-CDF tomeo via reaction ijutvi 1 .i< ) .. >l` `ormjtijn of a penta-cjF via reaction route 3 is not possible with this PCB and fait no additional penta-CDF was observed. None of the two hexachlorobiphenyls showed the formation of significant amounts of he*aCDFs. From the pyrolysis of 2,4,5,2' ,4' '-hexachlorobiphenyl, the formation of a major te'ra- and some minor penta-COFs was 01 .erved (see Fiqure 4c1. The tetra-COF <?*pected is the 1.3,7,8- substituted isomer formed vjj reaction rou'e 1; the pet ted penta-. jre 2,3,4,7,9- and 1,3,4,7,8-penta-CDf 'reaction route 2), and 1 .3,4,7,3-penr *- .reaction route 3). However, only the or~`ion of 1,3,4.7,3- and 5 ,1, T,7. >-i>**r j -. * F , I j be confirmed, the formation of 2,3,1.7 .l-omta-CTF rmimi-.j unLl>-ir The pyrolysis of 2,3,4,2' ,3' ,4' -hexachlorobiphenyl l*ad to 'n* m>-- *: > * * ,- * and a penta-COF (see Figure 4d). They were 1 dent 1 f ied as 3.4.6.>- , ; ' .. , . - penta-CDF, the isomers expected from the pyrolysis of this PCB vii ryjt`1 3, respectively. The formation of a penta-CDF vU reaction route 2 is not - '*i -1 nd witn this hexachlorobiphenyl. The formation of a hexa-CDF could not be confirmed. The pyrolysis of 2,3,5,2' ,3' ,5'-hexacnlorobiphenyl gave a major ind j nn-.r *,*t*\i- CDF and a major penta-COF (see Figure 4e). The major PCOFs were identified as .'.4.6,8- tetra- and 1,2,4,6,8-penta-CDF, the expected products from the pyrolysis of tms PCB via reaction routes I and 3, respectively. Again, the formation of a oenta-CDF via reaction route 2 is not possible with this PCB, and in fact no additional isoner was observed. The identity and source of the additional, minor tetra-COF remained unclear HONS 003397 figure 4 . Hass f ra flt*d - lLI i f 'Qff t { f ) ( ,i .t y( , J .t and 3' J*) of pyrolyied He*chlorobipnen/ls showing t-Un or >tr.i , ,jenM- a .V*. try . ,4,6,2' ,4* ,6* -, (c) 2 *4.5 .2\4'V . .1) ? , 3.4 , `. j ,4 - . ,. ? ,3.- , j ,4, j' ,4 ' , \ ' 'ftexdtnl orob ipfteny l. Column cndi t i.ms as in i i -el HONS 003398 Pyrolysis of 2,3,6,2' ,3` ,6`-heaachlorobfphenyl yielded three tetra- and r> ..tj- CDFs , ee Figure 4f) the number of isomers expected via reaction rout , and 2 react ion route 3 and 4 not possible for this i ...... in ,_jse of totra-CDr . f , ,ted isomers are 1,4,6 9-, 1,2,6 9- and 1'.d-' tra-; jf. Tin ''rxt e'-.nr: isomers were also observed from the pyrolysis of 7.) ,o ,1' ,F'-pentachlorobi phenv I Tsee ear!n* i. Therefore, the last eluting tetra-CDf was t*ra11vely iJtiiMn-j is 1,2.3,9-substituted isomer. In case of the penta-CDFs, the exoected isomers are l,2.4,tf,9- and i,2,4,6,9-penta-COF. The fciMt. on of 1 ,2 .4,8 ,9-penta-Cuf could be i.on firmed by co-chromatography with a reference imple `see Table 7'; the identi f- r ton of 1,2,4 ,fi ,9-penta-CDF is the first eluting isomer remains tentative. Cl Cl Q-& ci^i era 112,0^9-) Vpl. 8 197$ The major pyrolysis product of .1.4 ,>. J * ,4 ' , V <hcach I ,m *> i pom, i *r, idon-i* . .j as . 1. J ,t>, ? ,ii-he*a-C0f {see ri-iur is 'n>. <. i i> . , : ... formation of tetra- and penta-fDFs via rc-u t :*i > 1, o i - . this PCB isomer. Nevertheless, small amour's of prnt.r- ir. . fjrntity and source of these compound rt-,invo .jn. i..,. o&-d ----- S Cl Cl Ct^O^CI 2,3.4,578- MONS 003399 . U'>*s of hepta- and octJchlorotnpnerylj 'n. p/r yss of two hept.i- and one octa<.hlo--"?i; >'prvt .< : ill tnree >$ompr* jre nain i c^pcnent; c* .. i ;r-entc of py^n Iyjed sample* .i'1' . ......................... . '"o p/rolv$$ of 2,3.4,5' ,3' ,4'-hepf ^i ` i t * i'M "i . ' ` ' F I '.ijO' i.. 4 s . '. 4 ., '-pnnt -'`PF , fhp t>*D;?cpcj rr<v}in * *<* .. . > ['* .J i- `"e ''e<,*-CPFs, *.ny > '. ' . . . . ,' . tv.' ' K f l ;'l ' -I, ' . ' ' . ''P . 1 1 . . :.!*' 1 * - * i'Oi i- ,.i pit- oo ' * i-iDfitt'd i . t 'p.ltti-.jn MM.t'' i. nowt'M'i . . !' ` i ,, 3,4,0 . ' . '-n**p t <-> t r <*t'rp ) 1 . ' t j ;. , ' . J * r ,p * r - :.j ' . >' 'f y,\i1o .: 1 *-, nea- .*rul *'*:. t j* P.'F s '. ? .4 , ' ' ,b'-' i i . ................... -............ - i1 - ' ' t yt j nr. V ,'l * , i >. t un r'>utPs < I'm . , i-spi t'Ml f 0 Ilf I l- . . " " s ? * i }!> nt no* v i HUNS 003400 X4SS lra~ef penta-. cia-' "*vta- a. . ,.o and ;sO| of pjrol/iea hepta- ana t 'acnl oroD 1 ptlen/ i 4 slicing elusion of f fro., a. 2 .3.4,2 .3' .4 -. (b) 2.3 .4 , - ,2 ' .4' ,5 -nepta- ><* ic 2 , i ,i , 1,. ' , j , c . i - a .n i. rooipi cry I ColoAtn conditions as i n cigure I - HONS 003401 Hie pyrolysis of 2.3,4,5,2` ,3' ,4*,5'-octachlorobipheny1 yielded hexa-, hepta- ' octa-CDFs . .ee figure 5c). The main hexa-COF was confirmed -is me 2.3,4,6,' '.ubsti tuted isomer formed via reaction route I. In .id;tion. j minor he*a-CDF was tlso observed, the identity and source of which remained unclear. heptj-.DF was confi-med as the 1,2,.1,4,6,7,8- substituted isomer, the expected product formed via nMction route .1. The mass frajmentogram also shows the elution of octa-tOF, the pyrol/v. ,-odu..t formed via reaction route 4. Lone 1 us ions 'he pyrolysis of Hi individual PCBs was studied and shown to result m *he fnrma'i n of PUiFs via intramolecular cycl izations. The yields of PCDfs were estimated to be in the range of O.u up to several . Again the aipll.ation of hign-resolution (c and is documented as a necessity for the separation and identification of the PCUFs formed. *Pyrol>is of individual PCBs has proven tu be usrtul for the preparation of individual Or* in situations where only minute amounts cf isomer are required fur reference purposes, mainly in GC-M$ analyst*'. The formation of the PCDFs was found to ml low four general reaction routes involving the loss of Cl^. M^, and MCI wi'h or without a <. J-chlorme wigration oee Introduction). Due to the observ'd gent*, till/, it is possible to predict the structure of the resulting PCDFs. Ihe results support our earlier conclusion at pyrulvsis of Its is resulting in the formation of highly toxic compounds. Con* .*; .rot 1y, too *jf. ,u ' \ <i bur* ir-j of is a threat to the environment and should be .ivnt.led. Acknowle.Kefent . *t< thank Mr. A. <iarS and Mr. R. Mndahl, l,rs. . .V.ier , . . , i M. Morita, A. Poland and C.A. Machtmeistcr for mat mo avail if* refeience compounds used in the present investigat ion. HONS 003402 References 1. C. Rappe, H.R. Buser and H.-P. Bosshardt, -n. New fork A<_ad. Sci.. in yress. A. Poland, E.Glover and A.S. Kende, J. 5' j . t r.. ) 1. >.' . j. J A. Hoore, E.E. McConnell, O.W. Dalga-'d jn<j H..,. tM- '-i , *.rn in press. ti. 4. H. kuroki and r. Masuda, ihempsphere. 7, ;7I jJ4/8). ____ b H.R. Buser, C. Rappe and A. Gar*. Chemosohere, 131 id?';. 6. C. Rappe, A. Garl and H.R. Buser, Chemosphere, in prn-iv C. Rappe, H.R.Buser and H.-P. i;osshardt, Crefiiospnere, 7, 131 . l.i/Jj. 3. J.G. Vos, J.H.Koeman, H.L. van der Mais, M.G. ten Noever dp ilrau* and Food Coswet. Toxicol.. 8. tZb 1970). .nr *. k`. Qlie, P.L. Vermeulen and .1. Hutzmgwr, Cr,.'iiov,>rH`>, *v, ! -S l>77|. 10. H.R. 8user, H.-P. 3cssMrdt, C. Rappe and R rulahl, osunprp, 7, 119 M97B). 11. Dow Chemical Cor:>ui>. The t.-i .> ,n. iories if 1 <;. 12. R.J. Smith, Science, 2^2, 116n 1)78; 13. H.R. Buser, H.-P. Bossnardt and C. Rappe, Chemosphere, *, 134 ;I3',ij. 14. M. Morita, J. Nakagawa, . Aii/ima. S "irura and `J . 10. 7uM "viron ;'on?jm. ;..ai^o1., 13, 67 1 >77). 15. M. Mon fa, J. N ikagawa and . Rjp;:r . P'il 1. (1973). 16. X. Norstrom, K. Andersson and C. Pin:',?, r- ' , : *. .* . '.i* ' 17. A.S. kende, J.J. Wade, M. DeCamp 2. -'.Jde i"i ; `mi. ofjhe African Critical Soiietj. Los .. ; " H.R. Buser, Dissertation, University of .'e3, i' ll. M, Zell, H.J. Neu and K. Ballschmit*er, . n , f9 | )' 7 (Reeive4 la OK 8 P*bru*ry 1979) HONS 003403 /!. /!hU,- // /fa-5 b Christoffer Rappe*: Dioxins and dibenzofurans--Focus on two groups of substances [Dioxiner och dibensofuraner--twa sybstansgrup- per i blickpunkten]. Lakardningen, 76^ (1-2), 1979, p. 21-23. _ " ST. LCUIS * Dkn i8 professor of Organic Chemistry at the University of Translated from Swedish by the Ralph McElroy Co., Custom Division, 2102 Rio Grande, Austin, Texas 78705 USA MOMS 003404 Code: 239-2451 DIOXINS AND DIBENZOFURANS -- FOCUS ON TWO GROUPS OF SUBSTANCES Summary The toxioologioal effects of dioxins and dibensofurans are diseueeed with special emphasis on possible carcinogenic effects. The presence of these pollutants in various products is disclosed as well as the possibility of new formation, especially from ohlorophenols and PCB, particularly during combustion reactions. In the article the possibility is discussed of exposing people at work and in the environment. Dioxins are a group of substances which recently have attracted great interest among researchers as well as the general public. The disaster in the chemical factory near Seveso in northern Italy in July, 1976, was caused by a discharge of the exceedingly toxic 2,3,7,0tetrachloride-dioxin (TCDD). The quantity has been estimated at 2.5 kg. Fear of the same toxic substance was one of the reasons for the great commotion at BT-Kemi in Teckomatorp. Fortunately, these apprehensions have proved to be considerably exaggerated. In recent years, there has been intensive discussion in this journal of certain effects of both phenoxyacids and hexachlorophene (Axelson, 1977; Axelson, Sundell, 1977; Bystrom et al., 1977; Hailing, 1977; Hardell, 1977; Johansson, Wahlberg, 1977; Westerholm, 1977; Hardell, Sandstr&m, 1978; Kalldn, 1978). Since these substances have a direct association with dioxins and dioxin-like combinations, it may be relevant here to present an overview of the present state of knowledge. The polychlorinated dioxins (PCDDs) are a series of tricyclic r h /or, aromatics. The number of earben. atoms may vary between 1 and 8, and there is a total of 75 different-position isomers. The polychlorin ated dibenzofurans (PCDFs) are very similar to the dioxins, both with regard to chemistry and to biology. The number of PCDF isomers is 135 (Figure 1). HONS 003405 Page 2 From a chemical point of view, both the PCDDs and the PCDFs are quite stable molecules. The photochemical (light) decomposition appears to be the most important reaction; however, investigations in the .United States and in Italy have established that in and on the ground the half-life is one year (Young et al., 1976). under arti ficial conditions, a considerably quicker decomposition has been observed (Crosby, Wong, 1977), but it is uncertain how frequently these conditions may be found in nature. Like many other environ mental poisons, for example DDT and PCB, the PCDDs and the PCDFs have the ability to accumulate in the food chain. This applies to aquatic as well as to terrestrial organisms (Firestone, 1978; isensee, 1978). The substances concentrate particularly in fatty tissues and in the liver (Nagayama et al., 1977). The reason for the great interest in PCDDs and PCDFs is that certain isomers of these substances have proved to be exceedingly toxic, especially 2,3,7,8-tetra-CDD and some others with 4 to 6 chlorine atoms (Figure 2). All of these have an LD5q value of 1 to 100 yg/kg for the most sensitive animals species. A good correlation has also been found between toxicity and induction of certain liver enzymes. Moreover, noteworthy distinctions have been found in biological activity between the various isomers. A factor of 1,000 to 10,000 has been reported for isomers as closely related as 2,3,7,8- and 1,2,3,4tetra-CDD (Poland et al., 1976; McConnell et al., 1978). This shows that it is quite necessary to define carefully which isomer or iso mers of these potentially dangerous substances are found in various preparations and environments. Biological effects As far as sublethal and chronic effects of PCDDs and PCDFs are concerned, only 2,3,7,8-tetra-CDD has been investigated to any large extent. The typical effects in animal experiments are damage MONS 003406 Page 3 to the liver and thymus gland which, in turn, have caused effects upon enzyme activation and immunity defense. This may t>e the explanatign of why the joint exposure to phenoxyapid 2,4,5-T"and 2,3,7,8tetjja-CDD has been proved to produce vigorous synergistic effects in animal experiments (Allred, Strange, 1977). TCDD has also proved to be a very potent teratogen. Recently, several good summaries have been published regarding the most important biological investigations of PCDDs and PCDFs (IARC, 1977, 1978a, b; Moore, 1978; Poland, Glover, 1978; Vos, 1978). The possible carcinogenic effects of these substances are of special interest. In the course of the evaluation, which was made at IARC in Lyon approximately one year ago, it was found to be dif ficult to establish any actual evaluation because data were lacking (IARC, 1977). Since that time, a number of animal experiments have been concluded and published. All of these demonstrate that TCDD in small doses can produce tumors (Allen et al.,-1977; Allen, Norback, 1977; Di Giovanni et al., 1977; Van Miller et al., 1977; Kociba et al., 1978; Toth et al., 1978). Low general organ specificity has been observed in these experiments which may be interpreted to mean that TCDD has a general promotional effect. This is in good agreement with the results which were recently published by Kouri and Nebert (1977). Moreover, it may be noted that a mixture of 1,2,3,6,7,8- and 1,2,3,7,8,9-hexa-CDD proved to be capable of producing tumors in animal experiments (Holmes et al., 1978). Against the background of uncommonly vigorous biological effects for the PCDDs and PCDFs, it is surprising that it has not yet been possible to identify metabolites of these substances in any animal. The toxic effects are considerably retarded since the animals used in experiments only die after three to four weeks in spite of very maBsive doses. It has been found that the dioxins are excreted slowly just as they are, and the half-life is approximately one month for small rodents (IARC, 1977; Poland, Glover, 1978; Vos, MQNS 003407 Page 4 1978). For larger mammals, the half-life is considerably longer (D. Jensen, Dow Chemicals, Midland, USA, personal communication). Furthermore, it appears that for the more highly chlorinated combinations the half-life generally is longer than for the lower combinations (Nagayama et al., 1977), but great distinctions are found between isomers with the same degree of chlorination (C. Rappe, Y. Masuda, H. R. Buser, unpublished data). Occurrence of PCDDs and PCDFs Neither dioxins nor dibenzofurans have had any technical appli cation; however, they do occur as pollutants in a great many technical products. The phenoxyacid 2,4,5-T (now totally prohibited in Sweden) contains the dangerous dioxin TCDD. Use of this phenoxyacid started towards the end of the 1940's, and during the 50s and 60s it was generally used in Sweden for foliage control in the lumber industry. The greatest quantities and the products most likely containing the most dioxin were used in the war in Southeast Asia towards the end of the 60s (the defoliant Agent Orange). Analyses of civilian and military preparations from this time have shown that in singular instances TCDD contents of approximately 50 mg/kg (IARC, 1977) could be measured; a median value is considered to be 1-2 mg/kg. During the 1970s, the contents have been lowered as a result of the fact that the authorities in a number of countries have introduced res trictions (maximum 0.1 mg/kg) and most preparations now satisfy this rule. The chlorinated phenols have a comprehensive technical appli cation, for example in saw mills, as a discoloring agent, in pressure impregnation of wood products, in tanning of leather and as a bacter icide in the paper industry. In Sweden, the greatest quantity of chlorophenols was used as a discoloring agent in saw mills; however, this use has, in principle, been prohibited since January 1, 1978. HONS 003408 Page 5 The technical preparations are very impure (Nilsson et al., 1978) , and the contents of PCDDs and PCDFs are in the vicinity of 100t1,000 mg/kg. ~ _ The biological and toxicological picture is complicated by a great variety of various isomers. The principal preparations on the Swedish market contained approximately 20 different PCDF isomers (Rappe et al., 1978). The majority of these pollutants has not been identified or toxicologically tested. Imported pentachlorophenol has been proved to contain 1,2,3,6,7,8-hexa-CDD. A similar pollution situation is found for the polychlorinated biphenyls as well (PCB). Previously, these preparations were used i in a variety of different combinations, such as in transformers, condensers, hydraulic liquids, heat transfer liquids, paints, plas tics, foundry sand and paper for automatic copying (IARC, 1978a). In Sweden, they are now only permitted as dielectrics in condensers, but even here they will be exchanged for other products. However, this applies only to newly built condensers; all of those which are in operation continue to contain PCB--an estimated 100,000 units with a combined 2,500 tons of PCB. Even if condensers are completely closed systems, all of them sooner or later will have to be opened, which poses occupational and environmental risks. The PCB preparations themselves are a mixture of some 50 similar combinations; however, the technical products contain as much as 1-10 mg/kg of a mixture of PCDFs (IARC, 1978a), but the discrete components have not been identified. On the other hand, it has been established that the toxic activity of the preparations is parallel to the content of PCDFs (Vos et al., 1970). The bactericide hexachlorophene is manufactured from the same initial material as the phenoxyacid 2,4,5-T, and it may therefore contain the same quantities of the dioxin TCDD; by further purifi cation, the TCDD content has been lowered to 0.03 mg/kg or less in this product. On the other hand, hexachlorophene contains approximately 100 mg/kg of chlorinated xanthenes, the possible HONS 003409 Page 6 toxic qualities of which are entirely untested (Gothe, Wachtmeister, 1972; Baughman, 1974). . Formation of pcdds ana pcdfs ' By analysis of so-called fly ash from municipal refuse combus tion plants and industrial central heating operations in Holland and Switzerland, it has recently been established that this ash contains both PCDDS and PCDFs (Olie et al., 1977). The quantity varied but was on the order of magnitude of 0.5-1 mg/kg (Buser, Bosshardt, 1978). Corresponding analysis of the ash from the municipal central heating plant in Uraea showed no occurrence of these pollutants. The number of components in the fly ash is very great, 30-40 isomers of either PCDDs and PCDFs. Together with two Swiss col leagues we have identified the most common components; we did so in order to be able to make a dependable risk calculation. We found that the most dangerous PCDDs were only lesser components; however, the most dangerous PCDFs were the dominating ones (Buser et al., 1978a, b). The occurrence of PCDDs and PCDFs in fly ash demonstrates that these disagreeable substances can be reconstituted in the case of pyrolosis or combustion. He now also know that they are formed by incomplete combustion of chlorophenols (PCDDs) and PCB (PCDFs), and the small quantities in the fly ash have been formed by unintentional combustion. If this risk is to be eliminated, control of what is combusted or burned must be improved. Combustion of foliage or cutter shavings impregnated with chloro phenols has resulted in noteworthy quantities of dioxins, 100-1,000 pg/g chlorophenol. In spite of the fact that the relatively harmless PCDDs dominate in the smoke gases, it has appeared that when impure technical preparations are used during the combustion occasionally more than 10 ug/g chlorophenol is more formed of the truly highly toxic 2,3,7,8-tetra- and 1,2,3,7,8-penta-CDD (Rappe et al., 1978). MOWS 003410 rage 7 In the case of heating of PCS to 500-700C, large quantities of PCDFs are formed, up to 3-25%. Precisely as in the -case of the fly ahs the most disagreeable PCDF components dominated-(2,3,7,8tetra-CDF) (Buser et al., 1978c). This uncontrolled combustion of PCB is a very serious risk which must be taken into account in the handling and above all the destruction of the great quantities of PCB found in condensers both here and abroad. Groups exposed The most serious exposure of workers has happened in connection with accidents in the manufacture of 2,4,5-trichlorophenol or other chlorophenols. Up to the present, 14 accidents of this nature are known, and the one near Seveso was the most recent to occur. In this instance, even the civilian population was exposed. BT-Kemi has been the only manufacturer of chlorophenols in Sweden, but it has never produced 2,4,5-trichlorophenol--only 2,4-di- and 2,4,6-trichlorophenol. The number of workers exposed in these accidents is 500 to 1000. The most common symptoms are chloracne, liver damage, and heart and vascular diseases; however, a great variety of other symptoms have also been described (IARC, 1978b). The group of workers that has been studied most intensively is the 75 who were hurt in connection with an explosion at the BASF factory in Ludwigshafen in 1953. Of the 17 persons now dead, six died from various tumor illnesses^(expected number: 3). 'The number of stomach tumors was 4, compared to the expected 1 to 2 (IARC, 1978b). As a result of the comprehensive use of chlorophenols, large groups have been exposed to these preparations and to the pollutants found in them. Among the groups most exposed may be mentioned workers at sawmills, in the paper industry, and in tanneries. At many sawmills here in Sweden, previously shavings and other products were burned HONS 003411 Page 8 which had been treated with chlorophenol, but it is difficult, retrospectively, to quantify these potential risks (chlorophenols are now prohibited in sawmills). ~ _ As far as PCB is concerned, special attention must be given to the exposure which has occurred in the manufacture and repair of condensers, but also in connection with work with hydraulic oils and paint for ship bottoms. In December, 1977, a transformer burned in central Toronto. The firefighters and workers who fought the fire did not take any special protective measures. PCB is erroneously considered to be very resistant to fire. Subsequently, several workers have had various complaints. A testing of soot has indicated considerably increased contents of both PCB and PCDFs (the Toronto Globe and Mail, 1977-12-17 and Newsrelease Ontario, Ministry of the Environ ment, 1978-02-13). The most serious poisoning with PCB and PCDFs occurred in 1968, in southwest Japan. Because of a leak in a heat exchanger, a quantity of rice oil for domestic purposes was polluted with PCB, the so-called Yusho disaster. More than 1,200 persons have been classified as victims of this poisoning, all of them with serious cloracne. The content of PCB in the rice oil was approximately 1 mg/gi however, the content of PCDFs was approximately 500 times higher than normal (Nagayama et al., 1977); Rappe et al., 1977; Buser et al., 1978d). In an epidemiological case-control study, it has been demon strated that personnel exposed to phenoxyacids and chlorophenols as well have a clearly increased risk of being killed by malignant mesenchymal tumors of the soft parts (Hardell, Sandstrom, 1978). These results may be interpreted to mean that either both phenoxy acids and chlorophenols are carcinogenic or, on the other hand, that these effects occur due to those PCDDs and PCDFs which are found as pollutants in these preparations. The phenoxyacid 2,4,5-T contains 2,3,7,8-tetra-CDD and pentachlorophenol 1,2,3,6,7,8-hexa-CDD, both of which have caused tumors in animal experiments (see above). MQNS 003912 Pago 9 For the future evaluation of the suitability of the phenoxyacids as herbicides in agriculture and forestry, it is obviously absolutely necessary to establish what caused this increased tumor" frequency. As far as the chlorophenols are concerned, it may be noted that they continue to be used as bactericides in liquids for cutting, refrig eration, and grinding. It has also been discussed in various contexts to what extent the general public may have been exposed to phenoxyacids and TCDD, for example, during the war in Vietnam, and in north Varmland (Torsby). From Vietnam, there are reports of considerable increase in abortions as well as instances of primary liver cancer among the population that has come into direct contact with the sprayings (Ton That Tung, 1977). As far as perinatal mortality in north VHrmland is concerned, it has been the subject of a special investigation (Council on Social Affairs, 1977). Without entering into any detailed analysis, I do want to point to the fact that the word dioxin is not mentioned in this investigation. This is especially noteworthy against the background of: 1. 2,4,5-T being used in foliage control; 2. 2,4,5-T contained approximately 1 pg TCDD/kg (or more) at this time; 3. TCDD is considered the most powerful teratogen known and is fetotoxic as well (IARC, 1978b); and 4. TCDD may concentrate in the fatty tissues of ani mals (for example, elk, reindeer) eating sprayed vegetation. If any connections were found to exist between prenatal death, malformations, and sprayings, then the most likely avenue of exposure is by way of consumption of meat containing dioxin. This exposure was not discussed by the investigators. ' The increased interest in dioxins and benzofurans during recent years has resulted in much new material coming out concerning groups which previously had been occupationally exposed to these substances. Any total risk evaluation, especially for the long-range effects, is HONS 003413 Page 10 not as yet possible; however, IARC/NIEHS has a special program for these substances with planned meetings every other year, and within WHO work is proceeding with a "Health Criteria Document". Recent accomplishments within analytical organic chemistry have demonstrated that these disagreeable substances appear more generally than pre viously assumed. An increased level of knowledge concerning these substances is necessary in order that the risks may be minimized. HONS 003'*i'* RfTnc* ALLEN | It. 8ARS0TTI D A. van MJLLER I P. AMAHAUSSON 1.1. LAL1CK ) ): Mwviivilockai )>!,** 1* M*Akv mt diet Ciriltainin? tow JlveU Of I.J.7.8* Ntrin'M w*iJibuo.;*-*;fcin. Pood Comal Teilt4l-4t9i9l7 N0.1EACX D W: Carclnescnto potential ( the patycMoriMttd fcpfcenyla. On^m to ' Hwum CMmt. Ctod Harbor Ubo> morn 19TT _ ,, . alucd P m. strange j i: ne effem to mU and 7J.TJ wtlblar<HiNnipdto s vatopfep chithva wnWyM. AnA Eevtro* CMMI TmM fc 4ll4d9 (SIT AXllBON Ot ' the nffae* Lahartldnlnonn ?4t isii-isia, is7?. UNCSLLU PNMIO*VOttd*ond Llkartl*tfn8Mi 74t 2II7.NM, ???. AUCHMAN X W: Tc'nrtMtwoJihtiuu.p* Otoalto to the eavkoament. High rewdutinn kMCV*mctiy at th pie*,turn level, tkchk Harvard University 1974. Appeo- 4iCM C umI O USES M R. 10S3HARDT H P: PelycMo* Hem DRonatovrene ' anil Senatoe to 4rr Aaeh# kommenifer und JndaMrtoSto Ver8rennuafrenle*4H. Alto Ca* tom Lehenwn Hy# 4* :U-llJ 1974 - RAPPE Ct htoRUSfXtofk to ptoyehleit* Mad Abenea-p-dtoeln ,jmm found to Ay ZlTcHmtoJmwTi 145-in 1978a RAPPSC.UHDAhLR: Mttttfctoto* to pMjiMm1h`t4 f*------*-- 1--------- *- Ay itk Mt4 PCI pjrttoyt. Chcmoep.Ure r: 419-429 19Kb , ,, , . ,, -,fc/.P?UCt pMMito ..'poly^lwtoec.-d dtbtnsotoan* (PCD?*) S>* pytclym toPCtt.G*0'?>*r ?i tW-ll* :w* RAPPS C, GAdA A: Peyehlonr.atcd to. htPttoto^tt (PCUFll found Yuha md uvtd limiMM PCS. CSamMphwe 7: 4t-Ap 1*73 4 YETHOM 0.. LUNDOHEN M.. MEYER- U1 A..PALMDOROM; AMUdyo* mun to tort*t malformation and prenerti iwwtoWy to t/aemtend, LMtanldnlnper. 7* cjimwh A S: Environment!! tomtouton to JJ,?J*imWoi*.i-*iM*to tottift fTCOD). SdtMi 59S: 1557-1JJt 1977 Of OfOVAHNI J. VIAJE A. SIIMY D L, StAOA T J. JUCHAU >1 R: TomoMiwtlto>3 etotoy to 14.7.t-M*mMM4.ka*-pdtoiUn (TCOOI Mid Artdor 1254 to (U two iur* tyiim to mowk *ar. Itotl SikKm CfMM Tottoto It: 552*55? I9T7 PlftlSTONt Ot n U,7^tervCS*0oto. toBU>pam>to*to puMm: rovis*. Koto Bull (SiMkAtonJ 27: 41*54 1979 Page 11 GOTHQ R. WACUTASEISTeR C A: Synlhe* lit to U.4.5.7>h:*acl.fi'-ox*"ihiM. Acta Cturn Sear^J Z6: 752J 772 HALLING M; (uietttMl UNdMlM Mimm HMMhlarepltmel Myewre an* Mrtlt mat* formation, Ufoartfdnlnpon 74: MM4I, 7977, HAADELt L: Mallfnantmamtottymal tumor* and oxpoiura to ph*noayaaMao allnlaal obaarwatlon. tcAartldntoaan 74: 2TA> 2784, 7877. HAnOtLl t_. SANOSTDfiM a.: MalWlt mMonehymM tumors of toa toft parti and aupoaur* to phanonyaoto* or totloropAanelr, Ltoartltoilnn ?8t 1U91S34,1878. HOLMES P A. RUST J H. ILwHtIR W R, SHEPHER A ftf: La*i| term totCcto to TCOO and KCDD In m'rca and rati. Ab> tract 24 New Vw'1. Acad !ti< Science V/eck tow 2I-*Jom JO. 1974 ISENSKs A R: Bictecur.n:L.laa to TCOO. Ecto Bull IStccUwim) 77: 255*29: |97d JOHANSSON O.. V*AHL8RHQ AS.: Saraoma and elMiltali, LAitotolniin 74: 8is> 1877. koc;tia r kjyes o c. bsysr j t. CA...;eON B S. 0L>;A.i.3 PJ: L.v.y.wrm taalcolo'xc Mutoct to 2.1.7J.u.chtorodW Bcr.:o<>toor.ia (TCOO> kt-wreiwry aid. m>H. A^:tr;(t 25 New Yotk A<to Sei. Sc!> mt: V.'ceV Ium It-ton* 59. 1979 XO'JR! R. NEOERT D W; Ceneiic refi.h.:(uo to Wic.:?:ib!i4ty to ooiyeyciic-ayt.'oorbon* Induced .umart in the rnouM. OripM to Kudu Cancer. COM Harbor Ubo .rtlonf Jll-1.14 1977 KALLENB: Delivery reiuin emony hoepltal employee*, LUkirtWnlnpn 75: 3688-3670, 1878. McCflNKBLL E. MORRE i. HASUMAN I. HAItr.lS M: The comparative toaicHy to chtorinuted dibento-pelivtin itotne.a in mice Mid (tone* Toitd Appl Pharma, cto 44: 533-555 1971 . MOORS J A: The dioxin problem * ever. Hew. Real Boil (Slodthoim] 17: 154- 1*4 I9M NACAYAMA 1. MASUOA Y. KUKAf* SUNK M; DelcrminxMn to auiychlurlautcu dibcnstowreio in (wc to ibtieetk with YuxM*. Food Comret Toxicol 15: 195199(977 NILSSON C-A. NORSTR0M A. ANDERS* SON K. RAPPE C: Impvritie* ia cammer- OUE X. VXRMEULEN P L. HUTZINOER O: Oltorodibania p doaim and aMarodL SoaaohrMa two Iraaa ceatpooaMa toOy aah MOWS 003415 Page 12 Figure 1. The chemical structure of FCDDs and PCDFs. MONS 003416