Document G6YRpyBmzeRmgrLa2EGvXy8jr

y 'a by _/L|f * Allonen, Hannu, EskoTisalo, Jussi Kanto & Kaeevi Pihlajamaki: Inotropic /ty Action and Myocj><flial Uptake of Digoxin and Betamethyldigoxin in Isolated I Guinea ..................................................................... ........................................ 545-552 |L.t Ravshan Husain, Mohammad Mushtaq & Satya V. " C,irf>'D^//Eff(it of Manganese on Neonatal Rat: Manganese Concentra- tiorjf inc Enzymatic Alterations in Brain ...........................................................553-560 < Muj^tXa, R., T. Kleimola & J. Kanto: Pharmacokinetics of Mcthylergo- " -ij^fnetrine (Methylergonovine) in the Rabbit and Man............................................. 561-569 Sou, Nils E., Arne Froslie & Gunnar Norhejm: Chronic Copper Poisoning in Sheep. III. The Distribution of Soluble Copper- and Zinc-binding Liver Proteins of Lambs compared with Adult Sheep........................................... v.____ 570-574 j. Dyeing, F.rik & Tore Aune: Hexachlorobcnzene Induction of 2,4-Diamino- TV anisole Mutagenicity in Vitro .......................................................... ..................... 575-583 Mf.lander, A., K. Danielson, J. Vessman & E. Waiilin: Bioavailability of Oxazepam: Absence of Influence of Food Intake........................................... 584-588 0 ^ Letters to the editor C SUNDQUIST, HaNNU, hUp^^UffWlft^MCCTn^flEMlNEN, KAAR1NA UnPO & > Lennart 'KAUjyjJ^cLThe Effect of ljhiydr^reotoxine on the Adenylate in Homogenates of Rat Cercbr% Cortex ................................. 589-592 CHEVOSPMERE A. WolL K. Bunzl, F.^e, and W.lkschmidt B. Zimmerli undWMa M. Th. M. TuWG. M. Tillmanns N and O. HutzWjer N O- C. RappjwL Gara, H. R. Buser and HHRSosshardt t, A. rtffstrom and K. Andersson * A. Norstrom, K. Andersson and C. Rappe C-A. Nilsson and K. Andersson $ C-A. Nilsson and K. Andersson B. Chittim and S. Safe K. S. Parthasarathy and K. Unnikrishnan ffect of Ca2''-ions on the absorption of Pb2+, Cu2+, Cd2 + and Zn2 + by humic substances 215 Der Uebergang biozider Stoffe aus Anstrichen in die Gasphnse Tetrachlor-lsophthalonitril (Chlorothalonil) 223 Environmental chemistry of PCB-replacement compounds - v/ -- the metabolism of chloro-isopropylbiphenyls in f'sh, frogs, fungi and bacteria 231 Analysis of polychlorinated dibenzofurans in Yusfto oil using high resolution gas chromatography--mass spectrometry 237 Preparation of chlorinated diphenyl ethers from biaryliodo- nium salts 241 Studies on the formation of chlorodibenzofurans by irradia tion or pyrolysis of chlorinated diphenyl ethers 249 Synthesis of chlorinated 2-phenoxyphenols 263 Chromatographic properties of chlorinated 2-phenoxyphenols [Phenol; Chlorophenol; Chromatography; Mass spectrometry] 269 Photodecomposition of 2,5-dichloro-p-terphenyl, 2,4,6trichloro-p-terphenyl and 2,5-dichloro-o-terphenyl in solution 279 Bronchial dose due to decay products of 222 Rn inthe living environment DSW 378343 STLCOPCB4099705 C;'.mosphere ho. `j, pi, 231 - 236, 1977. Pergamon Press. Printed in Great Britain. anai.y:':i:i ok i*oi,\i:ui.<minati-mj pihkn'/iOkiikan:; in yiisiio on, ii::i;t; nicn iiicioi.iiTioN ha:; ciiuomatoghapiiy - ma:opkotiiomktiiy Christoffer Rappe and Anders GarS. Department of Organic Chemistry, University of UineSt 3 - J01 87 UmeS, Sweden and Hans Rudolf Suser and Hans-?aul Bosshardt Swiss federal Research Station CH - S320 Waderiswil, Switzerland iReccive-l in UK 7 April L>'77i accepted for publication 15 April 1977) - Introduction Poly-..-' .rinat.-i biphenyls . ' ) are Industrial chemicals now known to be widely istrii'il'd in tie enw ironm -nt. The commercial product1, are complex mixtures of at least different substances. The toxic effect aiid the bioaccumulation of the discrete PCB..'liners .! y reman abuly. L-2 In , ' 7os ,et al.. identified polychlorinated dibof.r.'furans (PCIMfe) as toxic impurities a Bure; >in PCIis at the ppm level, ^ and the same has also been reported for American and A. n apanese ,J..oe y Using packed-column GC'/MS, Bowes t al. found that the most abundant i'OUFs ne : the same retention time as 2, 3, i',8-tetra-CPi' and 2, 3>4,7,8-penta-CDF. 5 In lX>3 more than 1200 persons in South-West Japan were intoxicated by consuming a .irimerciai rice ji, contaminated with 1000 ppm of a Japanese PCB (Kanechlor)Nagayama et al. analvaed the rice oil (Yusho oil) and found 5 ppm of PCDFs. Consequently, the PCDF concentration in the Yusho oil was about 250 times higher than in ordinary Kanechlor, mm m m 1I 231 DSW 378344 STLCOPCB4099706 232 i.n. ' preparations. Nagayama ot^ al. also found tetra- and ponta-ODFs to hr most ahinukijit, lnil. they also found small amounts of the tri- and lioxachloro isomers/ Recently, Bowes et al. have reported that they found three isomers of both the tetra-CDF and penta-CDF, the dominating tetra-CDF had the same retention time on a packed column as 2,3,7,8-tetra- CDF.7 , -v . . - The toxic effects of the PCDFs are very similar to the:*' reported for the polychlorin ated dibenzodioxins (PCDDs), in both cases the 2,3,7i6-tetrachloro compound being the 12 8 most toxic isomer. ' ' Like PCDDs, both PCDFs and certain PCE isomers have been found to 29 increase cytochrome P-450 activity and a number of drug metabolizing enzymes. ' In this paper, we report on the analysis of "Yusho oil C" using glass capillary column GC in combination with different mass spectromc'ric techniques. - Experimental The clean-up of the Yusho oil (l. bg) wan p- forr.i'-l estv.nljoj J,v <t : : i - eluding alkaline saponification and chromatography on silica gcl.^ Final chromatography was Carried out on an alumina-microcolumn using 10 ml portions of 2$ and 50$ methylene chloride in n-hexane.^ The PCDF fraction was carefully evaporated and the residue re dissolved in 100 pi of n-tetradecan; . Similarity, a solution of synthetic 2,3,7,8-tetra- m CDF was prepared in n-tetradecane at a concentration of . jout 1 ng/yl. Aliquots of 2 pi of sample were analyzed on 0V-101 and 0V-17 glass capillary columns (22 m x O.36 mm ID) using an isothermal splitless injection technique as previously described.^ The columns were coupled via a fused platinum capillary, leading directly into the ion-source of a Finnigan 1015 D GC-MS (election impact source ?.t 70 eV). The columns were operated at 197C (OV-101) and 207C (0V-17) with a helium carrier gas pressure of 0.6 - 0.8 atm. A vaporizer temperature of 270C was used, the interface was at 250C. Mass specific detection (mass fragmentography) of PCDFs was carried out by monitoring molecular ions at m/e 270 (tri-CDF), m/e 34 (tetra-CDF), m/e 338 (penta-CDF) and m/e 372 (hexa-CDF). At a further stage complete El inass spectra were recorded using a Finnigan 4000 GC-MS equipped with a 6111 data system. ' DSW 378345 STLCOPCB4099707 -2,3,7,8 te t ra -CDF STLCOPCB4099709 II u. 2.13 Results and Discussion The mass fragmentograms using OV-lOiand OV-17- columns arc given in Rig. 1 and 2. The 0V-101 is a non-polax column with a good grouping effect aee->rding to the number "of chlorine atoms. The OV-17 is a semi-polar column, with more spreading of the positional isomars. Consequently ,. OV-17 appears to be better for an optimal separation of the . ' .s' isomeric PCDFs. Fig. 1 and 2 also allow us. to make an estimation of the num' r of tri-, tetra-, penta- and hexa-CDFs present in the Yusho oi] (suspected isomers, TabLel). In the case of the most abundant isomers, the discrete PCDFs could be identified by running complete El 'mass spectra. All the spectra were in agreement with published data, expected ion clustering and major fragmentation (M+-C0C1, M^COCl-Cl^). . Table I Humber of PCDFs in Yusho Oil Cl, Cl. Cl, Cl, Suspected isomers Identified isomers r ' Identified by complete MS, no positional assignment. Identical retention times were found for the major tetra-CDF peak and an authentic . sample of the 2,3,7,8-tetra-CDF (501 sec on 0V-101 and 557 sec on OV-17). By simple com parison of peak heights the estimate was made that 2,3,7,8-tetra-CDF amounts to at most ynfo of the total tetra-CDFs. Our investigation using high resolution GC strongly supports the assumption that 2,3,7,8-tetra-CDF is one of the main PCDFs in Yusho oil, an assumption so far only based on separations using packed columns. Optimal separation using high resolution gas chro matography is required when it is important to separate between a large number of posi tional isomers. .2 MI S-ii'ir *1 DSW 378348 STLCOPCB4099710 236 No. m Acknowledgments The authors are indebted to Dr. Yoshito Masuda, Fukuoka, Japan for the Generous gift of the Yusho oil and to Dr. J.D. McKinney, Research Triangle Park, USA for the 2,5,7,8tetra -CDF sample. Referen-es J.D. McKinney, K. Chae, B.N. Gupta, J.A. Moore and J.R. Goldstein, Toxicol. Apni. Pharmacol.. 36. 65 (1976). .2 J.A. Goldstein, J.D. McKinney, G.W. Lucier, P. Hickman, H. Bergman and J.A. Moore, Toxicol. Appl. Pharmacol., 36, 81 (1976). 3- J.G. Vos, J.H. Koeman, H.L. van der Maas, M.C. ten Noever de Brauw and R.H. de Vos, Fd. Cosmet. Toxicol., 8, 625 (1970). J.A.G. Roach and I.H. Pomerantz, Bull. Environ. Contam. Toxicol., 12, 358 (1974). G.W. Bowes, M.J. Mulvihill, B.R.T. Simonoit, A.L. Burlingame and R.W. Risebrough, Nature, 256. 305 (1975). - J. Nagayama, M. Kuratsune, Y. Masuda, Bull. Environ. Contam. Toxicol., 13. 9 (1976). 7. G.W. Bowes, M.J. Mulvihill, B.R.T. Simoneit, A.L. r.urliiigame and R.W. Risebrough, Paper presented at Workshop on TCDD, Milan, Italy. Oct. 23-24 (1976). .8 E.E. McConnell, J.A. Moore, J.K. Haseman and M.W. Harris, Toxicol. Appl. Pharmacol.. 37. 146 (1976). A. Poland and E. Glover, Mol. Pharmacol., 736 (1973) H.R. Buser, J. Chromatogr.. 107. 295 (1975)- H.R. Buser, Anal. Chem., 46, 1553 (1976). rt" t&'s* DSW 378349 A* STLCOPCB4099711