Document 6B6KV480pyaL6871xd25aB7B1

Chonoopiioro Iio, 5, p(( 231 - 2j6, 19"7- Peignaon Press. Printed n 3.-cit Britain ANALYSIS OF POLYCHLORtNATTN DIBSHZOFURANS IN YUSIlO Oil US INC RICH RESOLUTION CAS CHROMATOGRAPHY - MASS SPECTROMETRY Chrlatoffer Rapps and tndsra Cart Department of Organic Chaalatry, Unlrorslty of Oast S - 901 87 Coal, Swadan and Rina Rudolf Dusar and Hana-Paul Sonahardt Swiaa i'adaral Raasaroh Station CH * 9820 Vtdanswll, Svltxsrland (Sacaivad in CX 7 Aorll 1377; iocsptad for publication 15 Ap.'.l 1577) [1 troductlon PoljroIUortnatad blphanyla (PCBs) jxa Industrial chenicala now xnoto to la wlutly rlUtritmtsd in tha anvironaant, Tha caBerelal product* aro coaplai ai l,rti of at 1- at SO dlffsrtnt aubatancsa. Tha toxlo offset and tha bloaocuumlatlon of taa dlacrrt* PCS12 laoaari vary rsaarkably. ' In 1970 Vos t ldantiflad polychlorinated dlbansofurana (PCDFa) aa toxlo iapurltiaa In European PCRa at tha ppa la/al,^ and tha aaas has also boon papertad for Aaarlcan and Japanoas PCia.^'^ Cling packad-eoluan GC/HS, Bowoa t ^1. found that tha Boat abundant PCSFa had tha ia*i ratantlon tlaa aa 2, 3,7,C-tatra-CDP and 2, 3,4,7,8-psnta-CDF.^ [n 19M aors than 1200 parsons in South-West Japan vara Intoxicated by conaualng a oeaaarolsl rlca oil oontaalnatad with 1000 ppa of a Japansaa PCB (Kansohlor).^ Nagayana at analyisd tha rioa oil (Yuaho oil) and found 5 ppa of PCDPa, Conaa<iuantly, tha PCSP concantratlan In tha Yuaho oil was about 25O tloaa higher than In ordinary Kanaehlor *31 HONS 214390 an n ') Preparation*. Hagayama 1*0 foul'd tctia- and penta-CDF* to bo O0*t abundant, but they al*n found vhaIL amount* ot th* trl- and haxachloro lionori. Recently, Ecu** _t al. have reported that tbay found thro* iaomara of both thi tatra-CDF and panta-CDF, th# dcalnatlng tatra-CTP had the aana retention tie* on a packed column aa 2,},7,8-tatraCDf,7 Tlia torlc affects of th* PCDFa an vary ainllnr to thoia rport*d for th* polychlorin ated dlbanaodioxin* (PCODa), la both caw* th* 2,3,7,8-t*lr*ehloro compound bain* th* moat torio laoaar.^'2'^ Lika PCCD*, both PCDFa and cartain PCB iaomara hav* b**n fourd to increase cytochron* P-450 activity and a number of drug aataboliting anaymaa. 2 4 In thia papar, v* report on tha analyal* of "Tuaho oil C" uaing glaa* capillary eoi-zn OC in combination with diffarant aaaa apaotroaatrle technique*. i ! I I Th* elaait-up of th# Tuaho oil (l.bcJ am poiforaad aaacntialiy aa 'iir,-,: . .. 6 eluding alkaline aaponifioatlon and chromatography on ailica gal. Final chr:-\f fr-itv vaa carriad out on an alwaina-miorocolumn uaing 10 al portion* of Zf and 5^3* sathylazu chloride in n-hoxan*.* TTw PCI fraction vaa carefully evaporated and th* raallu* _-t- diaaolvod in 100 ul of n-tatradacana, Siailarily, a solution of aynthatio 2,7,8-t*tra cer wa* prepared in n-tatradaoan* at a concentration of about 1 ng/yl. Aliquot* of 2 tU. of aaapl* vor* analysed on OT-LOl anl 01-17 glaaa capillary column* {22 i j 0.^ to IS) uoing an iaothaxmal aplitlaaa injection technique as pravloualy daacribad.11 Tha column* war* coupled via a fuatd platinum capi1lary, leading directly into th* ion-tourc* of x FlnnigaA 101J B QC-IS (alaotion impact aourc* at 70 *V). Th* oolumnt vara operatad at 137SC (01*101) ant 2070 (OT-17) with a helium carrier gaa proaaura of 0.$ - O.S atm. A vaperiaar tamparmtura of 270C was used, th* intarface vaa at 2$0C. Haas apaoifio dataotion (mass fragmantography) of PCSFa vaa carriad out by monitoring oolecular Ion* at m/a 270 (txi-COT), a/a }04 (tatra-CDF), /* )}8 (pantn-CSP) and a/a 372 (hex*-CPF), it a further ataga complat* SI aaaa spectra war* recorded uaing a Flnnlgan 4000 GC-HS equipped with a 111 data ayataa. t HONS 214391 iS 5 M tu t Oo 6 i l: X. O Figure 1 . Mmi fre^aentosrau (OV-101 elect rn|itll u / coiuviti at 197C) of luubo oil ihowing elution of PCOFa (/ 270 trl -, u/* }0H - i,,uu-. u/o 1JU - ponta- ud /o 172 . boia-CDF). MONS 214392 r>j OV-17 m/e 338 m/e 304 m/e 270 30 min Flgart 2 : Hue feagaectograiu (OV-17 rl.icapllJeij . <>|unr< ot 207) of Imho oil tboulog #lutian of KDfi (/i ZlO - til-, /v w/o JJO |tfnta- and b/o J72 * hua-CHfJ, HONS 214393 Jio. 5 235 Results and Discretion Th* me** rnigreentograme using OV-101*nd OV-17 column* ax* gWen In FI*, l nd 2. The 0V-101 i* non-polr column vlth * good grouping effect according to th* njobor or ehlorln* atoms. The OV-17 lo * iemi-polar column, with nor* *pr**ding or th* positional liom*r*. Consequwntlp, OV-17 appear* to b* b*tt*r for an optimal (operation oC th* l*c**rlc PCDPa. Fig. 1 and 2 al*o allov u* to mak* an **timation of th* number of trl-, tatra-, pantaand haxa-CDTs pr**nt in th* Tuaho oil (*u*p*ct*d l*om*ra, Tabla 1). In th* cat* of th* ao*t abundant isomera, th* di*or*t* PCSF* could b* identified bp running complete SI mat* apaotra. All th* p*otra were In *gr**a*nt with published date, arp*ot*d ion clat*rlng and major fragmentation (M+-COCl, N+-CCC1-C1^). Tabla I Humber of FCDFe In Tuaho Oil Cl Cl }4 Cl 5 Suspected ieomera Identified iaomar* 669 244 3 1 Identified bp oompl*t* MS, no positional aa*lgnm*nt. Identical retention time* were found for th* major tatra-CDF poak and an authentic temple of th# 2, J,7,#-tatra-CDP (501 esc on 0V-1O1 end 557 t#o on OV-17). Bp simple com parison or peek height* th* estimate woe eada that 2,J,7,B-tatra-CDF amounte to at most JOJt of the total tetra-CDPe. ' Our inreatigatlon using high resolution OC etronglp supports th* assumption that 2, J,7,(J-l*tra-CnF is one of the main PCDF* in Tuaho oil, an assumption *0 far only baaed on separation* using packed oolumna. Optimal separation ueing high resolution gas ehronatographp io required when it is important to separate between a large number of posi tional ieoaera. MONS 214394 2J6 AcknowlcdCTMnta Th aut'nora on Indebted to Dr. Toahlto Xaauda, Fukuoka, Japan Tor the cuncroui of the Tuev.o oil and to Dr. J.D. XrKlnney, ftoaearch Triangle Park, USA for the 2.5,7,5totra -CDF cample. Referenced 1. J.D. HcKinnajr, X. Chao, B.H. Gupta, J.A, Xoore and J.B. Goldataln, Toileol. Aaal. Pharz.icnl.. j, 65 (1976). 2. J.A. Goldataln, J.D. McKinney, G.V. Luoiar, F, Hickman, a. Dorian and J.A. *'cort, Tori col, Atcl Pharmacol81 (1976). 5. J.G. Voa, J.H. Koeman, H.L. van dar Kama, H.O, tan Hoavar da Brauv and S.3. la Voa, Fd. Coamot. Toalcol., 625 (1970). 4. J.A.G. Hoach and I.H. Fomerante, Bull. Environ. Contam. Toalcol.. 5JS '`.t*!), 5. G.W. Bovoa, X.J. Xulvihill, B.F.T, Slmonalt, A.L. Burlingame and 8.W. ?.lcacr.>n, , Hthttf., 2&. 505 (1975). 6. J. Naayaae, X. Kurateune, T. Xaauda, Call. Environ. Contam. Toileol. i, > (1976). 7. G.H. Bovaa, X.J. Xulvihill, B.B.T. Slmonalt, A.L. Burlingame and R.W. Rlaabrough, Fapar pr*ranted at Workshop on TCDD, Xllan, Italy. Oct. 25-24 (1976). 8. K.E. KoConnall, J.A. Hour*, J.K. Baetman and K.W, Harrle. T2illj_All. Fharraeol.. jj, 146 (1976). 9. A. Poland and S. Glover. Xol. Pharmacol.. 2> 736 (1975). 10. R.B. Buoar, J. Chromatoar.. 107. 295 (1975). 11. B.B. Buaar, Anal. ffliaa.. 1555 (1976). MONS 214395