Document 5bV6w9Ngyp7rvwd2aryYky5BJ

* ", 7 ' > / { . . k .w l. **j* V. .* .' V.__ .. >1^_ -/ ` ---- - -t * _._ ' _ % r 7 Chetesphere S o . 1 , PP V sj - 115 1573 F e riu o o a P r e s s . P rin te d - C r t i i B r i t a i . *< i- / : ); ^ -flft F oaitm c:: c? po lycslo rish d d o eszo fttuis (p c if s) ixlCn THE PTH01Y3IS 0? PCPs RECEIVED mat 11 1978 J- E BROWNJit. r- Hans R ud olf S u se r ar.d E a n s-P a u l B o ssh a rd t Sw iss Federal R esearch Statio n CE - 2320 V id e n s v il, S w itz e rla n d and C h ris t o f f sr r a j ; s Ie p n x tr*rr o f Organic Chem istry, U n iv ersity o f Urea S - J C l 37 C re a, o'-aden (R eceiv ed in UK 3 Ja n u a ry 1973; a c c e p te d f o r p u b lic a tio n 5 Ja c u a ry 1573) In tro d u c tio n P o lych lorin ated b ip h sn y ls (PC2s) ara in d u s t r ia l chem icals o f vide use and now mown to ' w idely d is tr ib u te d in the e n v ir s m e a t. The cc n n sro ia l products an* complex c l r tu r s a of at l e i 3t 61 d if fe r e c t su b sta n ce . Irne to th e ir e x t r a s * s t a b i l i t y in e c o lo g ic a l s y r te n s , the* use o f ? H s i s now r e s t r i c t e d to se a le d system s lin e c a p a c ito r s and t r a n s fe r r e r s . However, p rio r to 1572, ?C2s doe to t h e ir food thermal and chem ical s t a b i l i t y were used in a v a r ie t y o f other a p p lic a t io n *; in p a r t ic u la r the use a s h eat t r a n s fe r f l u id s and c a stin g w ires v-is a sso c ia te d with tho th em r i s t a b i l i t y . 7<ry c lo s e ly r e l a t e d *o the PCHs are the p ' l / o r c r i i n t s d b ip h e n y l* ( P l u s ) , sen e c f which hn.* bee.t on.od a s f l a n * r*to n -r a n t s . Of s p e c ia l ir.tsn e.vt i s H ire M arcir I~ - c o r Fire- M aster - vrnc- -re shown tc c : : n 3 t n n ia ly o f 2 , a , ; , 2 ' . 4 ' , 5 '- h a u a b tr n ;`.ip h in y l.~ I n t o x ic a t io n tn t h i s ?12 h as beer. d_r-iroiy a s s o c i a t e d w ith n w iie -o p re a d a r r i c c i . r u r a l c a la m ity in. >> 11 i r v - * * ;* i. t ! ? fi ill 1;i K-.i i I;/. i t :': KI,*.i t i: V ENP 010312 783123 10? Ko. 1 111 KLcroo'.-rc lv sla Quartz n in l- a s p o u ls s were zad s from q u artz tu b in g u x ir g a g-an-oxygen bu rn er; the len gth s o f th ese ampoules were 25-30 the in t e r n a l d iam e te rs 3 *4 1=2 ^ 4 the ra lu r.e s 0 .3 nil. E sin g a r i c r o - s y r in g e , 10 ^1 o f a sta n d a rd s o lu t io n (c o rre sp o n d in g to 10 o r 100 u * compound) was placed in to the tip o f an ampoule. A fter conplete evaporation o f ths solven t with the a id of a s l i g h t v acu u s, the a r p o u le s ware c lo s e d u s in g a v e ry sm all f l a r e ; c a re was taken. n o t to h eat the t i p s c o n ta in in g the compounds. "Die volume o f 0 .3 r I a i r in an arp ou le was k e p t ap p ro xim ately c o n sta n t. The m olar r a t i o s o f PC3 to oxygen in an arp o u le were about 1:75 and 1 :7 .5 - r aro u n ts o f 10 and 100 ug o f FC3, r e s p e c t iv e ly . The q u artz m in i-arp o u lea were p la c e d in an e l e c t r i c a l oven (n a x . te r p . 1CC0 C) p reh eated to tem p eratu res ra n g in g from 550 to 3 50 C . The te n p e ra tu re v a s c o n t r o lle d w ith a therm ocouple in an arpoule placed next to the sam ples. H eating p erio d s ( t i r e between p la cin g a sample arp o u le in to the oven and rem oving i t ) were k ept c o n sta n t a t 60 s e c . The t i r e r e q u ir e d to h e at the m in i-arp o u le s up to a te n p e ra tu re 'within 20C o f the p r e s e t valu e was around 55 see, the tin e of a sarp le a t actu al p y ro ly sis tenperature thus around 5 se c . l i t e r rem oving and immediate- c o o lin g to roon tem p eratu re, the t i p s o f the a r p o u le s were broken and 200 y l o f benzene added. 1 2 -u l a liq u o t was used d ir e c t l y fo r a n a ly s is . F u rth e r d il u t io n was re q u ire d f o r sam ples w ith low d eco m p o sitio n o f PC3s to overcome o v e r lo a d in g e f f e c t s o f the ZC-X5 sy ste m . Some s a r p l e s were elean ed -u p cn an a lu o in a - c ic r o c o lu n n , u s in g 2Ji and 53> methylene c h lo rid e in a-h exare to se p a r a te ly e lu te ?C3s and PCTFs. 12 OC-iTS A n aly sis A n alyses were c a r r i e d out cm" a F im ig a n 4000 quadrupole GC-M3 in stru m en t eq u ip p ed with electron -im pact ion -source and a F im ig a n 6111 d a ta -sy ste n . 07-17 g la s s c a p illa r y columns of 2p and 5^ r le n g th (O.36 im ID) were c c u p led v i a a p latin u m in t e r f a c e le a d in g d i r e c t l y in to the io r .- sc u r c c . Tns c o lu m c o n d itio n s ware an f o llo w s : 1CTC, 2 n in iso th e r m a l, 1 5 /= in to 1 4 5 , 5 '/ = i ~ tc 2 J0 CC f e r the 23 n 07-17 column; 1 0 0 , 2 min is o th e r m a l, 2 0 / 3 iu to 1 6 0 , 2 */m i= to 2 ;0 fo r the 50 c 0V-I7 column; helium c a r r i e r g as a t C .20 and I . 4O a t , r e s p e c t i v e l y . Samples ware s p l i t l e s s l y in trod u ced with ths v a p o riz e r a t 2cOC. GENP 010313 783124 * ii'i >in iian m fio. 1 117 Bain bexacfcloroblphenyls i s Arac ia r 1254? i t i s o f in toras i to confirm the presence of 23?7S-tatra-CD? a s i or the two panta-CDFs in th is complai mixture. The 2, 37?6-teira-CHP i s not completely sparatad os th is column. from another tatra-CD? isomer. She tetra-CDP forsed froB 2, 41^ 2 ' , 4 * to' -bexaghlogoblghenyl vas not found to h present. In case of the major isem srs, the discrete PCITs csnld he id e n tifia i by marrair g Vcosplete 1 aass spectra, i l l s a ss spectra showed Intense milecular lens with the expected ion clustering due to the chlorine isotopes and the ch aracteristic fr a ^ e sta tio n fo r rCDFs with formation of K+-CCC1 and M+-CCC1-C12. Pyrolysis of additional ccmso*^d<i idditionaly ve have studied the pyrolysis o f 2( 6t 2' f S>-tetrachlorchi;hsnyl and of P ireaaster 2P-6 (n aisly 2, , 5, 2 ' , 4 * 1 5, "haxabroaobiphanyl). Tatrachlorobtphasyl formed at 550C one di- and one tri-CD? isoaer at lev els of 1.6 and 2. respectively. The tri-CDF c a st he famed in a rearramgesant. i t 700C, the tetrachlorsbiphenyl va3 completely destroyed and no FCDFs were found. Tiranas te r B?-o was also completely destroyed at 7C0C, hut a t 600C new caapausds vera formed, one of which could he a tetrahrcncdlhenzofurzs (K +-480, 3 r 4 ; c a jo r fragrant h+-3r_ ; other fragments M+-Br and M^-COBr). In analogy vlth the corrasponding I iPC3 isorex, i t seess s e s t lU csiy*that i t i s the 2 , 3?7 S-tatra-3DFi Tho amount forsed i s about quai ta the asount o f tetra-CE? forsed frem the correspcndisg PCB, Conclusions the resu lts reportad in th is paper suggest that uncontrolled burning of PCBs can he an ioportant anviromental ssurce of the hazardous FCDFs. Although PCBFs have nst yet been found in the enrireosent, they have been id en tified in f l y ash from municipal incin erators and industrial heating f a c i l i t i e s . M o r e o v e r , fisgayama at al.~ ^ have feurd highly increased lev els e f PCSFs in the r 33 associated with the Tusho accident in Japan in L 'c3* and one of the rain components v is a l30 the 2, 37,3- te sr 2.-C lF .^ In sp its of being partly banned, large volumes of ?C2s are s t i l l in use, especially transformers and eap arite rs. In Sweden the amount now in use in capaciter is about 2500 zztons; a J i r i l s r xmeunt applies fo r Switzerland a c ts r iir g a survey by the Swiss Federal Off i c f >hlie >itlth. It ir vidant that a ll disposal o f ?C3s I h s u li be carefu lly 783127 GEKP 010316  Ho. l i--- /-> 119 13- I . O li*, P .l . 7 ia a u la and 0. H utainjer, Cr.gnsaahgre. 5, 455 (1577). 1 4 . E .S . Buaar and E .-P . Boashaxdt, K it t . G*b. L l - s n it t a lu n t r s . u . ~v j. . in jrr*sa (1972). 15 J . K. ru ratau n * and Y. Kaauda, P u ll. Syringe. Contan. T o rlc o l. 15 9 <1976). 16. C. 3 a p *, A. Gara, H.H. B u a*r and H.-P. Boashardt, Ccenosnhgre. 2J1 (1 9 7 7 ). .7 . .'T t >S .r -r,D .. ,^-o ";IS ;V t> r ic!- Vir- . tnvs-c'-; m y_>^-=r a--: *r*W | S c-t 783128 r; V*f-- *.*>* -- 'S" fc' fr L" M'j w,v-- ^ y '* o 25* mf f l . . - o !L O i--* L S 'S 2 - VP S t ^ V^L >".-Vxil^--&i.i"'",ivZ'u .