Document NEbYvv0dEeNRy4ovE3zE2B6DE

hauw Uiflu ttfCM Vir, ri /.* detected no chlorinated dibenzofurunx in an Aroclur I2M) preparation at a detection limit or 1 p.p.m. FrMW'nation and examination of the identical Aroclor 1260 inCBstudy confirm their findings based on (he stated limit. buMevcal the presence of II chlorinated dibenrofurans in (he preparation, having a total concentration of 0.8 pg g~` PCB (Table II. The same workers also found diethyl ether extracts of the Clophen A60 and Phenoclor DP6 to be much more toxic to chick embryos than diethyl ether extracts of Aroclor 1260. Our study confirms those findings on the basis of chlorinated To ' Time (min) 20 l,b O; 1 St a____ ISO 200 2S0 300 350 Fig. 2 o, Cas chromatogram of a Traction of Aroclor 1254 containing a mixture of chlorinated biphenyls, dibeniofurans, aod naphthalenes. Identities or peaks are given in the text. A, Mass spectrum of peak 2. a tetrachlorodibenxofuran. v *. *i i V Jibemofuran contem: the identical Clophen and Phenoclor contain it and 17 times more total chlorinated dibeniofurans. respectively, than the Aroclor 1260. A gas chromatogram showing components derived from the Aroclor 1254 obtained in 1969 is represented in Fig. 2. The .omponenls were eluted in the second 400 ml Florisil fraction md recovered from the alumina column in 20" methylene .blonde-hexane. Each oT the numbered peaks was trapped <s described here, and identified by mass spectrometric matysis. A nominal mass plot of the high resolution mass -pectrum of peak 2 is shown in Fig. 2. The plot includes alt he ions with elemental compositions ranging to the maximum mpirical formula C,,H,0MCI,,,CV*C,. The molecular ioh luster at nominal m/e 304-310 fragments by successive losses >f Cl to yield the ions at mle 269-275 and CO to the ions at nit 241-245. A minor loss of Cl from the peaks at m/e 269-275 tlso occurs to yield the ions al mle 234-238, followed by CO elimination to mle 206-210. The group of pens-, in mle 152-154 arc the doubly charged molecular ions. An identical spectrum w3* obuined from an authentic standard of 2.3,7.8.(ctrachlorodihenrofuran. This latter compound has a retention time identical to that of peak 4. Peak 2 is, therefore, a positional isomer. The accurate mass measurements for the characteristic ions arc within 2 ppm. of the calculated exact masses, Peaks identified on this chromato gram and their retention times relative to dicldrln areas follows- a mixture of telra- and pcntachlorobiphenyl (1.02): letracltloro- dibenzofuran (1.30); pcntachIorobiphenyKI.46): teirachlorodi- benzofuran (1.57); hcxachloronaphthalcne (1.75); penta- chlorobiphenyl (I.R6); hcxachloronaphthalcne (2 001; and heptachloronaphthalenc (3.46). An aliquot of combined fractions derived from the same Aroclor 1254 was treated with diazomethane lo assess whether any chlorinated ortho-hydroxy, biphenyls (prc-Turans) were present. Gas chromatographic analysis of the sample before and after treatment resulted in identical chromatograms, As large quantities of PCBs have entered the global environ ment"'**. it may be assumed that the contaminant dibenzofurans also have been released in proportional amounts, Their per- sislence, effects, and significance remain to be determined. We thank J. A. Burke. M. L. Porter and J, G. Vos for discussions; A, S. Kende for standards of chlorinated di- benzofurans: and F. C. Walls for assistance with the mass spectrometry. This work was supported by the Canadian Wildlife Service. National Science Foundatiun. and NASA. Guald W. Bowls* Canadian Wildlife Sen ice. Micham. J. Mulvihill Toxic Chemicals Section, OrroHo, Canada KiA OH3 Br.XNO R, T. SlMONtlT A. L. Buftt.INGAMt Space Sciences Laboratory, University af Californio, Berkeley, California 94720 " . R, W. RiSEBKOUGH Bodega Marine Laboratory. University of California, . Fsdrga Bay, California 9492J Rtttivtd Fibrvkry IJiMcaptad Majr H, |fT5. *Prwni addirn: California Walar Rruwrcai Control Board. OTWiion of Plannint ind XcwircH, Uli Nmtli Sircar. Sacramento. California *5*14. Stolen. t, and Bovin, J , Xttutt, Hi. 3I2-5I3 (1474). > Ktxman. J. SI., Hjddt<jfth, R. H.. and Bijktcld. M. F. (. 1. Bio/. Ct/rr.. a. m-3ll (1971k JGiJbcrt>on, M., and Kfk, R., C*. FM Smt.. M, 3>4-]36 (1974). 4 Hi||lnBOth*m. C. R.. tl a/., .Wara, 229. 702*705119411. 11pafichu, C. t, Dima, F. L.. and Rowe. V. X-, Food Cotmti. Tour , 9, 40MH 0911 h Vot, J. C. Kocman J, H,. Van dar Maat. H. L-. ten Nrcvcr da liauv, M. C., Voatn. di.dGa V. ormt,wRm- rH. m./Wr* PrCrat*at.rp|r,. Torlr., I, 927-933 103'127(19721, i |4T0|. * ipntt.'G. W., Srmoflcii, B. R.. Burlintamc* a. L., da Lappa. I- W.. and R<* bcmi|h. R. W., Cmnr94*. HUk Ptftp., 5. I9l-t9t (|9J)k liufltmifi. R. and Mexlton. M.. Cmv,ram, Htr* Fifty, 3. 27-15 1I47.M. * Bati|Kman, R., and Mcwlton. M.. A4w. Cfcrm,. [19. 92-104 M Report n2 4.5-TlETCcurhaOflkro(tha Pratidani, Science Ad'uoijr Commiiief. Office of Scknc* and Ttchnu^ty, Ma'cW. 14711. 17 Jensen. S.. and Renter L.. Amkio. 1. 91-91 I [472[. tl Fimtont. D-, Rett- J.. Brown. N. L., Barron. R. P.. and Damico, J. K.. J An. Off. -W*r. CW., j}, " Porter, M. UiW Bwtke, 1. A.. J. Am Off. a*Jh. Oif.. S4. M?6~MU I'tTIl if Burlingame, A. L., Olvrn. R. W, and McPKcrron, R. V., Ait. Afau Spate., 6, 10) 3-1054(14741. MitHti. I. C. T .Ind 9aroBm, A- F-.Cap/'iwi. utih Fifty.. J, 21-31 II9TJ1. tT Bowat. G. 'A' * and JonkaL C. J-. / Fir*. FrJ. B*/ Can. tin tha prcitl. r* Jcnicn. /idiMhu A, O-. Oltion, M,. and Ottrflind. G-. Statef. 224, 247*230 <rw>. i1 Knaman. J. H., tan Noc^tr da Btta, M. C.. and da Voi, R. H.. Sittrt, 111. M26-ri2f 11499k t* KiMbrouill, R. W,, Rcickc, P,, Prakall, D. 9. Harman. S, G-. and Ki>s*n, M. N., 119. [041-1(01 (1491k HONS 205784 1* C44*3 l*H*aa tv* H*v t lao (.id *4 lh |Vtet#v fv>.>hv* i,, I Vox et at.* detected no chlorinaled dibenrofurans in an Aroeior 1260 preparation at a detection limit of I p.p.m. r/acliorwimn and examination of the identical Aroclor I2M) in our study confirm their finding* based on the stated limit, hui/BkeuI the presence of Jl chlorinated dibenrofurans in the prsi^Jiion. having a total concentration of 0.8 pg g'1 PC'S On Ok It. The same workers also found diethyl el her extracts of the Clophen A60 and Phenocior DP6 lo be much more toxic to chick embryos than diethyl ether extracts of Aroclor 1260. Our study confirms those findings on the basis of chlorinated w 10 Time (min) 20 300 350 ftg. I a, Cas clironiatpgiam or a ftaction of Aroclor 1254 containing a mixture of chlorinated biphenyls, dibenrofurans, and naphthalenes. Identities of peaks are given in the lent, ft, Mass spectrum of peak 2, a letrachknodibcnrofuran. dibenrofuran comcnr, the identical Clophen and Phenocior contain 11 and 17 times more total chlorinated dibenzofurans, respectively, than the Aroclor 1260, _ A gas chromatogram showing components derived from the Aroclor 1234 obtained in 1969 is represented in Fig. 2. The components were eluted in the second 400 ml Florrsil fraction and recovered from the alumina column in 20% methylene chloride-hexane. Each of the numbered peaks was trapped as described here, and Identified by mass spectromeiric analysis. A nominal mass plot or the high resolution mass specirum of peak 2 is shown in Fig, 2. The plot includes all the ions with elemental compositions ranging to the maximum empirical formula CitH,0"CV,CV*Ct. The molecular ion cluster at nominal mle 304-310 fragments by successive losses of Cl to yield the tons at mle 269-275 and CO to the ions at j mtr 241-245. A minor toss of Cl from the peaks at ml* 269-275 f also occurs to yield the ions at mle 234-238, followed by CO elimination to mle 206-210. .- The group of peaks ut m'e 152-154 ere the doubly charged rm-lcvutar ions. An identical spectrum was nhJ.iinctl from an authentic standard of 2.3,7,8-tctrachlnrtKiihen/nfuran This tuner compound has a retention time idcnlicul to that of peak 4. Peak 2 is, therefore, a positional isomer. The accuruie mass measurements for the characteristic ions are within 2 p p.m. of the calculated exact masses. Peaks identified on t his chroma togram and their retention times relative to dieldrin are as follows: a mixture of tetra- and pemachlorobiphenyl (1.02); tctrachlorodibenrofuran (1.30); pcmaehlorobiphenyft 1.461: tetrachlorodi- benzofuran (1,57); hcxachloronaphthalcne (1.75): penischforobtphenyl ft,86); hexachloronaphthalcne <2 00): and heptachloronaohthalenc (3.46). An aliquot of combined f- telions derived from the same Aroclor 1254 was treated with diazomethane to assess whether any chlorinated ortho-hydroxy- biphenyls (pre-furans) were present. Cas chromatographic analysis of the -sample before and after treatment resulted in identical chromatograms. As large quantities of PCBs have entered the global environ ment"'", it may beassumed that the contaminant dibenrofurans also have been released in proporlional amounts. Their per sistence. effects, and significance remain to be determined. We thank J. A. Burke, M. L. Porlcr and J, G. Vos for discussions; A. S. Kcnde for standards of chlorinated di benrofurans: and F. C. WaHs for assistance with the mass spectrometry. This work was supported by the Canadian Wildlife Service, National Science Foundation, and NASA. . GtXALD W. Bow-rs* Canadian Wildlife Service, MtCHAfL J. MULVttlll l Toxic Chemicals Scelioit, Onatca, Canada K1A OHS Bixnd R, T, Simon tit Space Sciences Laboratory, A. L. BuxunoAwr University of California, Berkeley, Californio 94720 Bodega Marine Laboratory, University of California, R, W. RlJCBXOLiC.il Bodega Bay, California 94923 Reniicd Ftbravy U: irnctca Mir It. I1J. Frctent addeaif? California water Retnuicct Comml Itotrd. Oiaigion of PianArng ftftd Rticarth. I4U Ninth Sn$et. Sacramento, California 951(4. I Newton, I., and Bogan. J.. Aa/arr. 24ft, 512*SI) f 19741. 1 Kirun.J, H^HitHlftinih, R. H-. tnd tfijitvtM. M. F. 1. J.. Biot. Comte* . I, 'Oiibtrtton. M-. nd Ha(t. R,,C*. Ftd Not.. II. 154056(1974). * Hiitiitbeiltlm. O. It., rr ot,, Vaftrrf, JJO. 702-70) fIfftlh * SpliKliUr C- L,, Dm, F. L.i and Ro*. V, K,,food Coimrt. Tostit.. 9. 405-4(2 turn * Vot. J. 0- Kotntn 1. If., Van dr Mt4i. H. I... in Nmki 4 Betxiw, M- C . and d< Vot. R.H-./Md OfMfr. rorfe.l, 923-9)1(1970). 1 Vot. J. C.. fRWM. Writ frr,, |, (05-1 (7(19721. * ftowt*. C. W., Simone*. B. R , Burlingame, A- L-. d* Lapp*, ft. W,. and Rn< ftrntl|h. R. W. r*<ntom. Htrh frets,.y (9t- (91 (19?)h * ftiu|hmft, R. tnd Metelton, M., Environ, HI*ft frr27*l!> fl9Ti|, i* Baughman. R., and MeKhoti. M,, Ad* Chrm (20. 92*104 (|97)|. II RfPOflon 2.i.t'T(hicullt S thf Seirnct AdvjioryCammttlet, Offist of Stkft^g Thrtpkt|y, March. 1970. f IthMi- 5 . and RtfAbetg, L.. Ambm, ). 9?-9)t(9?2). 1 fjenwiK. D., Rim. J., Brown, N: C-. Barron, (i, f., and Damo. J N , t. An. Of. Antijrt, Cbm., 55.13-93 J j97J,. . i* Foiiar. M. L.ftnd Burkr.). A . J. A is Off. AoJrt. Cbm.. 54. MIA- (4)1 |i97l *9 lutimilnH. A- L.. OIma. R. w. and McPhtrfon. R. V.. Ad*. Sfmu 5mif , ft, I0SJ-1039 J19741. *Nthel. I. C. T.. and SiioRm, A. F,,Emitnm, HftA I. JlOl (J91J). ' Rowel, O- w,, and Jankil, C- J../. F4* Art. Bd Com. ]in th< prmh * Jcntco. 5.. JoIwuH. A. O . Oliton. M , and OMHiiaf C.. No*mr, 214. I4M (1969). 4* Kmrur. I. H.. im Negs 4o fttav. M. C.. and d* Vp$. R. H . V- *rr. Hi. I I2ft-J 171119991. * RlMftrov|h. R. w.. Rtierw, F,, Peak all, D, ft. Herman. 5. O. and Kievan, M. N . Nmiterr. 220. JO9I-M02 Piialad ia Unit iMtpi * Miwf krai | id gs tat |iw #t ftm hMrh**t*< aah HONS 205785 mm