Document p2ZbwmEakXw1YayavEDjyqvZd

c P V*. 5, P 4W - 4, 1973. Ltd. Mata* la Orest Britain. oo<>-9i5/T/O5Oi-O4i90oa .00/0 MOTICE: This material may M protected by copy"*" unncuia* ar pouacumximD Dnmarmj nmm n m in aid pcs motrsn Iw Budolf Burner and Bane-Peal Boeefaardt Swles federal Research Station Cl - 8820 Wldsnsvll, Switaerland ad Cfcrlatoffer Sapp* and Boger Lindahl Department of Organic Chsniatry, Dnivarnity of tea 3 - 901 87 teas, Swedan (teceivud In UC 24 Apn1 1978; accepted for publication 27 April 1973) Introduction Ply iata and flu* gases of mnlclpal incInaratore and of an lnduatrlal heating facility wore shown to contain tha haaardoua polychlorinated <Ubonao-p>dlorina (PCDDa) and dlbeaso- furana (PCDfe) in addition to othar chlorinated cespoiaida . ' "e fly aah fron two different faailltlea In Swittorland thawed a renarfcably almllar dlatrlbution of tha PCSD leonere. ^ Tha aajor PCDD leonere found in eeaplee froa both facility ve were tho.e formed In the pyrolytic diaerlsatlon of the aoet cnanon chlorophenatee, nenely the 2,4- 41-, 2,4.8tri-, 2,3.4, 8-tetrm- end pentaehlorophenate, suggesting these coMnnly used pzodaote ae precursors to tha PCBDo. Tha known toxie PCDD leonere, each as 2,3,7,8-tetra-, 1,2,3,7,8- penta-, 1,2,3,8,7,8- and 1,2,3,7,8,9-heaa-CSD were present aa minor components. In addition to PCDDa, tha fly aah fron both facilities showed tha presence of PCVs ___ 2 ___ at a similar level as tha PCDDa. In all, 133 positional leonere exist for the PCZF'e, and sane of thee# are about equally toxie or biologically active as tha noat tozlo PCDtt. 410 OSW 033931 STLCOPCB4017893 420 lo. 5 Tbla la aapanlally tm f tba 2,37.S-Utr>, 1,2,3,7,8- aad 2,3.4,7,-psnt*-car.4'5 OoHHialal iihlampiwola km baan found to aontaia PCBDa aad PCBPa la tba ranga of tai to bndnda of pyn.4 fOVi bava baaa InrolTad in a ssrieua intoxication la Japan la 19M, oallad tbs Yuabo Aiaaaaa, 7 ' a tad thay bar* baaa aaaoolatad vltb polyoMoxinatad biphenyls (PCBa) la Alob they ara usually praaaat aa traoa iapuritiss a* tha ppa laval.5 Nla an industrial abanloals of vlda uaat thay ban baaa aaaoolatad vltb a vorld-vids nanlnlnatl m lasantly, aatloaa van takaa to raduoa or baa tbalr uaa. Xa a previous paper, va above! that pyrolysis of PCBa eaa raault la tba fonatloa of HVi at tba paroaot level.* Slaoa a largo portion of tha uaad PCBa may ba dlapooad bp iaolaaration, tbla fonatloa of PCWa may havo aavironontal sigolflcaaco. Ia addition to PCBa, polyohlorlnated diphenylsthars (PCBFIa) oould oaaa Into oonaldaration aa poaalbla precursors of PCBPa. Va havo ahovn that tba tbanal oaovarolon of PCVBa Into PCVa ia of tba aaoa 'rdar of aagnl tuda aa that froa PCBa.11 for tba pnoant, va oooaidar PCBa aa a aora probabla source for tba hasardous PCBPa dua to tba such largar production volune of tba PCBa as conparad to tha PCBPSs. In tbla papar, va raport tba anal/ala of PCBPa In tvo fly aab aaoplaa. 11 though va do Mt glva tba eoaplete atruoture of all laoners praaant, va abov by high-raaolution gaa ohraatograpby and nasa apaotroaatry that aoat of tba aajor PCBPa In tbaaa fly aab aanplta van also fornad in tba pyrolyaia of coanorcial PCBa (iroolor 1234 and 1260). Tbla finding gives atrong support to tha assumption that tha PCBPa found in fly aab an originating froa tba uneaatrollsd burning of PCBa. attraction aad aurlflcmllan of fir aab aanlaa Tba extraction and purification proeadurs uaad baa baaa pravloualy described.^ Tba SMS aanpls extracts van uaad in tbla study aa for tha identification of tba PCBB iaonara. ^ WlorourrolTala of PCBa iroolor 1234 and 1260 (100 ng saoh) vara pyrolyzed at 600C in separatequarts einl- aapoules. fta aaaat pyrolyaia oonditlona and tba clsan-up prooadun uaad ban baan DSki 033932 STLCOPCB4017894 Ho* 3 431 described.10 Irtraeta of previously pyrelysed 2,4.5.2*.4',5'- d 2,4,6,2*,4t6'-b<naehloro> biphenyl Mn lnalrnr* for oanparlsom. The following PCDF 1sonars won obtained! 2,3,7,8-tstrs- and 2,3,47,&-penta-<3ir as gifts froa Or. J.9. MoElaney, and 1,2,3,7,8-panta-CHF aa a gift froa Or. 1. Poland. Tha l,2,3,4,d-panta-COr woa prepared froa tha oorrespondlng PCOT bp a Pd-catalysed oyollaatlon.13 In addition, a mixture of 2,3,4,6,8>penta, 2,3,4,6,76-hexa- and 1,2,3.4,6,7.d-bopta-nF wan obtained by chlorination and deaninatioa of 37-dlaalnoboaaofnren. Thia mixture contained a minor enmt of l,2,4,6,7i8-hera-CHP aa veil. Tfi fl ImlTtll A finalana 4000 quadrmpele CC4f instrument quipped with electron-Lapset ion mom and a Flanigan 6111 data eyetea waa uaed. The aaaplaa ware analysed on a 30 a 0.37 a 0T-17 glaaa capillary coltan coupled to tha aaaa epaetroaater via a glass-lined atainlasa ataal tuba of low internal lianater (0.3 mt IS). In a fixat phaaa, complete aaaa apeetxa of Individual PCOPa were recorded (1.4 aao/acan, a/a 35-470) using tha data ayetea. Tha eoltam conditions ware aa followsi 120, 2 ain isotharaal, 20/nin to 180, 5/min to 230C. In a oaoond phaaa, the aaaplaa ware reanalyzed with optlaal isoaar aaparmtloa ueing aaaa specifie detection (aaaa fracaentography) of PCSPa by aonitorlng aoloeular loaa at a/a 270, 304, 336, 372 and 406 for tha tri- to haptachloro coapounda. Tha coltH oonditioaa this tlaa warai 100, 2 ala loothermal, 20/aln to 160, 2/ain to 250C. Individual rCl#a wore found to eluto la tha retention tine rangee indicated in Figaro 1 end 2. loaners in the extracts were ldwtlfled by co-chroaatography with tha reference caapowda. In tha pyrolyaia and fly ash aaaplaa aiaor quantitlea of polychlorinated naphthalenes (Pda) were observed at levels of one tenth to one fifth of tha PCSTa. These onapmuie give a response at tha a/a values listed above due to M%6 Isotope peaks, e.g. penta-d(M*-29S) at a/e 304. Host of the Pda observed elute prior to tho retention tine ranees of tha corresponding PCSPa. k differentiation between these enapoissda ie easily aahieved by observstioa of their oaaploto aass epootra (presence of M+, naaber of Cl's aa determined froa tha ieetepe oluatar and the typical fomentation with foraatloa of K*-COC1 for Pdfs OSW 033933 STLCOPCB4017895 'fra a tba pjTolyaio o f PCBa a rt illu a tra ta d balov fo r tha 2 ,4 '5 ( 2 't 4 ,5'-hazaehlorobipha&yl STLCOPCB4017896 No. 5 423 10 Tte quantifications given la the previous paper ladle*ta, that the throe reaetloa tehialaa have about equal probability la eaoe of the 2,4,5.2',4*, y-hexachlorobiphaoyl. 2,4,6t2',4'^'-Bexaehlorobipheojl la an iaonar not usually found la eoMerelal PCBe.^ Pyrolysis of thia compound reeultad In the formation of a tatra- and a penta-CSP In about equal aamints The tstra-CXP expected la the 1. 3,7,9-eubstituted isomer foraed by reaetloa 1. The formation of a penta-HW has to Involve a zearrangeuant; this leaner could be tha 1,34,7,3-penta-CIiy foraed by reaetloa 2 or another penta-CBf laoaer foread In another laailamaaint The foxantloa of a poota-CUf without any rearrangement according ta reaetloa 3 la not poaaibla aad no additional pentm-COT waa obaarred. 2,6,2'.fi'-Tatraohlorobipbaayl did ylald a di- aad a tri-CDF. Tha dl-CBP is aoat likely the 1,9- substituted laoaer foraed according to reaction 1, the trl-CBF la ezpeoted to be the 1,4,9- substituted laoaer foraed by a rearrangement (reaetloa 2). A trl-CIV foraed by reaction 3 la net poaaibla, and tha elution of an additional iaoaar waa not observed. Very few PC3JF standards are preeeatly available. However, micro-pyrolysis of individ ual, synthetically avsllabla PCB laoaars la quarts aiai-aapoulaa could be very helpful aad convenient way of preparing aaall amounts of PCDF laoaara for use aa qualitative referanca coapounda in analyses of various staples. V# are currently Involved in such a prograa, where tha structure of tha products free tha pyrolyaes are studied by coaparison with PCDFa prepared by other known methods. rotation of PCBFs from the PVTolysls of cotrclal PCBi Commercial PCBe (iroolors, Cloptoena, nienoclom, Kaaachlora) eonalst of a multitude of Individual PCB laoaarei theoretically there exist 209 laoaara, in practice up to 100 have been observed in coaaerelal PCBs.1^'1* In the present investigation, we have studied the pyrolysis of two coaaerelal PCBe, Aroelor 1254 aad 1260. Aroelor 1254 mainly eoaaiata of trl- to heptaehlcrobiphaayla and froa thasa wa eaa expect the formation of aoao- to hexaCWs according to reactions 1,2 aad 3, Sotaaae 1. Aroelor 1260 has penta- to oetaehlorebiphenyle aa tbs aajor conatltuenta aad froa thaae wo oaa expect the formation of trl- to hepta-CDFs. DSW 033935 STLCOPCB4017897 424 Wo. 5 Xa 1, mm fra^aatofnaa aho* tba alutloa of tri- to bapta-CSTa la the pyrolyaed Aroolora. With Jxoalor 1294 (Ticure la), memo- to paata-COTi van fnraoil (elution of tba nooo- aad di-CSTa not abowi) at a total level of approx. 2jt rolatlTO to tba PCBi with Aroolor 1260 (Tlgoro lb), tri- to bapta-COTa for-- d at a slailar level. Ia oaao of tba aajor laoaMra, tba dlaexete TCSVa oould ba Identified la both aaaplaa by nastier ec^l*ta aaaa apaotra. Sl^lfloaat quantities of txl-CWa wax* foxaad froa Aroolor 1294 aad tba elution of up ta 17 laoaara eaa ba obaarrad. Aroolor 1294 did alao predaea aono- aad dl-C07i. Ia oaaa of tba talia ll>a, si#UXloaat quantities vara foxaad froa both Arooloro. Slallar pattaxna with tba aaa aajor tatra-CDF iscners vara observed la tbaaa two pyrolyxotao. Ooa of tba aajor talia Plti la both oaaaa la tba extxsasly toxic 2.3,7,3-tetrm-CII7 (peak 44) aa abovn by on nhxn--tnataphy wltb tba aatbaatio ataadazd. This PCD7 la aoat likely foraed froa 2,4,9,2'l4,.9'-baxaoblorobipbM>7l (a aajor constituent of tbaaa Aroolora) by raction 1 or froa 2,4,3,3',4'-poataehloroblphsayl (alao praaaat la tbaaa Aroolora) by reaction 2,3,7,3-Tatra-COf mom not coapletely resolved on tbia ooluan froa another tatra-CST (paak 49) Wltb pyzolyaad Aroolor 1294, 6 aajor aad aboot 19 alaor tatra-CUTa vara obaarrad. Heat of tbaaa laoaara vara alao foznad wltb Aroolor 1260 but aoaa la raduead aaouata, notably tba paaka 94, 47 aad 46. tba tatx*-CS7 (paak 27) foxaad froa 2,4,6,2',4',6'- , , . -bazaoblorobipbaayl and tentatively idantlflad aa tba 1 3 7 9 tatra-CUF could oaly ba proaant aa a alaor coapooant. Apala, alallar patterns vara obaarrad for tba paata-OQ7a In both pyrolyaia aaaplaa. Ooa of tba aajor laoaara (paak 99, not separated froa peak 94) la both eaeeo haa an Identical retention tlae aa ana of tba pants CDFa foxaad froa 2,4,9,2',4,,9'~hesaohlorobiphanyli It la praa--bly tba 1,3,4,7,6-aabotltoted iaoaar foxaad by raaotion 9. Both, tba vary toxio 1,2,9,7,6- and 2,9,4,7.6 pail a CB7 (paak 60 aad 66, respectively) vara present la tbaaa aaaplaa at alanlfloaat 1avals. The foxaar could bo a product froa 2,3,4,2',4'9'-bexeehloroblpbanyl zooultlac via reaction 9, tha latter froa 2,4,32,,4,,3'-beauhloroblpfcaayl via raaotion 2 or froa 2,3,4,3,2',4,,3,-baytaehleroblphaayl via raaotion 1. tbaaa hexa- aa4 baptaabloroblphiyla barra bean rapartad aa ooastitnanta la ocanaroial TCBa.14 tba 2,3,4,6,6a4 tba 1,2,3,4,6 pail a I, IV (paak 61 aad 62, respectively) vara praaaat aa alaor unapnimita DSW 033936 STLCOPCB4017898 hopta- 200 haxa* T ---230 panta- Mra* --I-- 210 trl- CDFa ~l-- 100 (JO OT-17, / 270, 304, )J4, )72 w>4 404) (twain* slullaa Of trl- to kafta-ors u a) Arrears** Uaalar 1734 4 h) nmlj4 Araalar 1240. P**k lAaatlflcatlona aaa Uxt. gaaaltisltlaai 0.1 U 2 T l.t. CSW 033937 STLCOPCB4017899 0.1 ppp, ra a p o e tlro lr. Thla la aboot ooa th ir d to ooa h a lf o f tha la r a l o f tha PCDOa praaant STLCOPCB4017900 f aSo 1 So ' 3o 1 So * l Maw twmi|WH mount alutloa of m- U k*U-Ora la tha Or i* of a) aa laiuatrlal baatla* raoUltr mr u, 04 k) a nalalpal laolaantor at Mrlok. Goatltlaaa mi paak BMbarlna aa in near* 1. laaaltlrltlMi 0.2 to 2 T f... 3 DSW 033939 STLCOPCB4017901 St I s & ! f s Ii fi+ 5 t i i ! f r i Hfc> S 1 l O vji STLCOPCB4017902 He, 5 429 extent, duo to tba maontxollad burning of WBa. Contrary to tha PCDDe, in eaao of tho rcifi, fomd tho mt toale loaner* to bo the aajor conatituonto la fir aah ao wall ae ia tho PO pyrulyaatea. Conooyiontly, tho dlepoaal of PCBe try laciaoratloo ahould bo care fully controlled In order to nlnlnlso oBeirnmontnl ond occupational oxpoouro to tho haaardeua /Ufa. Vo thank tea. J.9* Hnllanoy and A. Poland and Nr. A. Gam for tho gtnaroua gift, of tho PC9P tandnrdo. Baforancoe 1. C. Olio. I T. Tameulen and 0. Butalngar, Chonowhere. , 4)5 (1977). 2. 1.1. Buoor and I.-P. Boaahardt, Hitt. Cob. labanan. u. Hr*.. , in praaa (1978). 3. H.l. Buaer, H.-P. Boaahardt and C. Bappe, Ch--oaphara. Xi 165 (1978). 4. A. Poland, S. Glorer and A.S. Eaoda. ,T| fltfl i 7hMn 251. 4936 (1978). 5. J.9. HoKlnnoy, K. Chaa, 8.1. (hipta, J.A. Hooro and J.A. Goldateln, Toxicol. i--i. Him.. 65 (1976). 6. C.A. Nilsoon, A. BorstrOn, K. Andaraaon and C. Bappo ia Pantachlorophaaol i Choniotrr. Phamacolonr and torlromental Torlcoloar. K. Bangs Bao (Bd.), Btr. Sel. Baa. Sarlaa Tol. ii, Plasm Praaa, Bov York (1978). V. J. Bagayana, N. Xuratama and Y. Haauda, Bull, BitIron. Con*n, T?il9Tli 12> 9(1976). 8. C. Bappo, A* Gam, H.l. Buaar and H.-P. Boaahardt, Chasoaphara. 6, 231 (1977). 9. G.V. Bovaa, H.J. Nulrihill, B.B.T. Slnonait, A.L. Barllngana and B.V. Hiaatrough, Batura. 256. 30) (1975). 10. H.l. Buoor, H.-P. Boaahardt and C. Bappo, Q>--noo^of. j, 109 (1978). 11. H.B. Buaor and C. lappa, unpubliabad rasulta. 12. A. Gam, feiraralty of taaa, unpubliahod roaulta. 13. 0. Hutalngar, 3. Safa and Y. Zltko, atrr of PCB'a. Chapter 2, CHC Praaa, Claraland (1974). 14. H. Zoll, H.J. Bow and K. Balloohnltter, & 69 (1977). DSW 033941 STLCOPCB4017903