Comment on" Occurrence and bioaccumulation of organochlorine

May 1, 1989 - Comment on "Occurrence and bioaccumulation of organochlorine compounds in fishes from Siskiwit Lake, Isle Royale, Lake Superior"...
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Envlron. Sci. Technol. 1989, 23, 617-618 Registry No. Tributyltin chloride, 1461-22-9; tributylstannylium, 36643-28-4; water, 7732-18-5;polyethylene, 9002-884; Teflon, 9002-84-0; polypropylene, 9003-07-0;poly(viny1chloride), 9002-86-2; perspex, 9011-14-7.

Literature Cited Waldock, M. J.; Thain, J. E.; Waite, M. E. Appl. Organomet. Chem. 1987,1,287-301. Lawler, I. F.; Aldrich, J. C. Mar. Pollut. Bull. 1987,18, 274-278. Gibbs, P. E.;Bryan, G. W. J. Mar. Biol. Assoc. U.K. 1986, 66.767-777. Thain, J. E.; Waldock, M. J. Water Sci. Technol. 1986,18, 193-203. Matthias, C. L.; Bellama, J. M.; Olson, G. J.; Brinckman, F. E. Environ. Sci. Technol. 1986,20,609-615. Meinema, H. A.; Burger-Wiersma, T.;.Versluis-de Hann, G; Gevers, E. Ch. Environ. Sci. Technol. 1978,12,28&293.

(7) Maguire, R. J.; Carey, J. H.; Hale, E. J. J.Agric. Food Chem. 1983,31, 1060-1065. (8) Meador, J. P.;U’Ren, S. C.; Salazar, M. H. Water Res. 1984, 18, 647-650. (9) Blair, W.R.;Olson, G. J.; Brinckman, F. E.; Paule, R. C.; Becker, D. A. An International Butyltin Measurement Methods Intercomparison: Sample Preparation and Results of Analyses. National Bureau of Standards, NBSIR 863321,February 1986. (10) MacCrehan, W. A. Anal. Chem. 1981,53,74-77. (11)Hasebe, K.; Yamamoto, Y.; Kambara, T. Fresenius 2.Anal. .-., Chem. 1982,310,234-238. (12) Kenis, P.;Zirino, A. Anal. Chim. Acta 1983,149,157-166. (13) Bond, A. M.; McLachlan, N. M. Anal. Chim. Acta 1988, 204,151-159. I.

Received for review April 15,1988.Revised manuscript received September 13, 1988. Accepted February 8,1989.

CORRESPONDENCE Comment on “Occurrence and Bloaccumulation of Organochlorine Compounds in Fishes from Siskiwit Lake, Isle Royale, Lake Superlor” SIR Recently, Swackhamer and Hites reported (I) new results concerning bioaccumulation of organochlorine pesticides and selected polychlorinated biphenyl (PCB) congeners in fishes. Three comments should be made. First, as regards to Table 11, where selected PCB concentrations are shown, it is surprising that PCB congener 2,2’,4,4’,5,5’-hexachlorobiphenyl (IUPAC no. 153),which is known to exhibit a rather high log KO,(octanol-water partition coefficient) of 6.92 (2),is missing. PCB-153, as well as other diortho derivatives, is a very significant component of PCB residues. Other authors reported values for congener 153 in marine biota samples, e.g., Duinker et al. reported that this congener accounted for 25% of 17 PCB congeners quantified in porpoise tissues (3) and L. G. Hansen reported that this congener was 20% of 14-18 PCB congeners quantified in freshwater eel, deep-sea fish, and eagle liver (4). Another comment concerns the authors’ statement (I) that a quantitative comparison could not be made for PCBs because earlier studies measured total PCBs (usually expressed as Aroclor 1254) and in their paper the quantitation is based on selected PCB congeners. In regard to that point, we would like to note that our group (5) has recently published an intercomparison between quantitation of total PCBs (as Aroclor 1254)versus selected PCB congeners (28,52,101,118,138, 153,and 180) in several marine biota samples. A fador of 3.17 has been found that can be used for correlation purposes between new data calculated by using selected PCB congeners and old data which used total PCBs. This approach can be used for the values of congeners 52,101,118,138, and 180 of Table I1 (I) (a value of 20% has been estimated for congener 153, and congener 28 has not been considered because values are usually below 4% in fish). By using the factor of 3.17 (5)to the sum of these six selected PCB congeners of Table 0013-936X189/0923-0617$01.50/0

11, a total PCB value around 7 pg/g for white fish and lake trout will be obtained. Further, this value can be added to Table 111; therefore, an intercomparison with the PCB content from other data is feasible. Now it is obvious that the sentence of the authors (I) indicating that PCB concentrations have decreased with time, from 34 pg/g (indicated by the authors in Table 111) to 7 pg/g (our approach), is correct. A final comment is related to the model of BCF-log Kow applied by the authors ( I ) , who stated that it was only a rough approximation of bioaccumulation and had completely failed for PCBs. The reason why this happened is that most of the PCB congeners that bioaccumulate in fishes have log KO,above 6 (2) or (as DDE) close to 6 (6). It is quite evident that no linear correlation has been found by the authors (1) because the correlation between the bioaccumulation factor and the octanol-water partition coefficient losses its linearity above log KOw values of 5-6 (7). To overcome this problem, other correlations have been proposed, i.e., quadratic terms have been added to account for steric factors as well as terms of metabolism (7). To sum up, it can be stated that a correlation between physicochemical properties and bioaccumulation will only be feasible if different factors are considered. Registry No. 2,2’,4,4’,5,5’-Hexachlorobiphenyl, 35065-27-1; biphenyl, 92-52-4.

Literature Cited

0 1989 American Chemical Society

Swackhamer, D. L.; Hites, R. A. Environ. Sci. Technol. 1988, 22,543.

Hawker, D. W.; Connell, D. W. Environ. Sci. Technol. 1988, 22,382. Duinker, J. C.;Knap, A. H.; Binkley, K. C.; Van Dam, G .

H.; Darrel-Rew,A.; Hillebrand, M. T. J. Mar. Pollut. Bull. 1988,19,74. Hansen, L. G. In Polychlorinated Biphenyls (PCBs): Mammalian and Environmental Toxicology; Safe, S., Ed.; Springer-Verlag: Berlin, 1987;pp 15-48. Porte, C.; BarcelB, D.; AlbaigBs,J. J. Chromatogr. 1988,442, 386. Mackay, D.; Paterson, S.; Cheung, B.; Neely, W. B. Chemosphere 1985,14,335. Envlron. Sci. Technol., Voi. 23, No. 5, 1989 617

Environ. Sci. Technol. 1989, 23, 618-618

(7) Esser, H. 0. Pestic. Sci. 1986, 17, 265.

Damla Barcelo, * Clnta Porte, Joan Albaigis

concn, +!g of fish lipido

Environmental Chemistry Department CID-CSIC Barcelona, Spain

S I R We are pleased to respond to the above comments and to provide additional clarification of our study ( I ) . Regarding the first comment, we regret that we were unable to include all PCB congeners in this study and that congener 153 did not appear in our results. We did not imply that the congeners on which we reported data were the only components of the PCBs in the fish. We are not able to determine the percentage of congener 153 from our present data. We are, however, able to estimate total PCB concentrations in the fish by knowing the concentration of selected congeners and by knowing the percent composition of those congeners in Aroclor standards (2). We were able to use this technique to estimate total PCBs in a related publication on PCBs in Siskiwit Lake (3). The results, which can be used to compare our results with other published PCB concentrations in fish, are shown in Table I. Finally, it is clear from our field data and from the studies quoted above that PCB bioaccumulation in fish is poorly approximated by a simple linear relationship to KO,. Although we reported a significant correlation (r2= 0.46) between log BCF and log Kow(see our Figure 2) ( I ) , it is clear that KO,is only part of the picture. It remains to be seen which other physical or chemical properties (or other factors) are most important in controlling bioaccumulation in fish.

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Environ. Sci. Technol., Vol. 23, No. 5, 1989

Table I. PCB Concentrations in Fish from Siskiwit Lake, Isle Royale, MI

LT sm LT med LT lg LT xlg av LT

4.6 6.9

WF sm WF med WF lg av WF

5.7 11 7.2

6.6 9.9 3.9 6.8

Exoressed as Aroclor 1254.

Registry No. 2,2',4,4',5,5'-Hexachlorobiphenyl, 35065-27-1; biphenyl, 92-52-4.

Literature Cited Swackhamer,D. L.; Hites, R. A. Enuiron. Sci. Technol. 1988, 22, 543.

Mullin, M. D.PCB Workshop, U S . EPA, Grosse Ile, MI, 1985. Swackhamer, D. L.; McVeety, B. D.; Hites, R. A. Enuiron. Sci. Technol. 1988, 22, 664.

Deborah L. Swackhamer School of Public Health University of Minnesota Minneapolis, Minnesota 55455

Ronald A. Hltes" School of Public and Environmental Affairs and Department of Chemistry Indiana University Bloomington, Indiana 47405

0013-936X/89/0923-0618$01.50/0

0 1989 American Chemical Society