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McCarty, P. L. J. Environ. Eng. Diu. Am. SOC.Civ. Eng. 1980, 106-114. Schnitzer, M.; U. Khan, S. U. “Humic Substances in the Environment”; Marcel Dekker: New York, 1972. Pflug, Z. Z. Pflanzenernach. Bodenkd. 1980,432-440. Wolkoff, A. W.; Larose, R. H. J . Chromatog. 1974, 99, 731-743. Rudling, L. Water Res. 1970, 4, 533-537. Baker, R. A. J . Am. Water Works Assoc. 1966,58,751-760. Stanlake, G. J.; Finn, R. K. Appl. Environ. Microbiol. 1982, 44, 1421-1427. Stecher, P. G. et al. “The Merck Index”, 8th ed.; Merck and Company, Inc.: Rahway, NJ, 1968. Smith, J. G.; Lee, S.; Netzer, A. Water Res. 1976, 10, 985-990. Bollag, J. M.; Liu, S. Y.; Minard, R. D. Appl. Environ. Microbiol. 1979, 38, 1, 90-92. Manem, J.; Bruchet, A; Fraisse, B.; Maloney, S. W. Presented at the International Symposium on Analytical Methods and Problems in Biotechnology (ANABIOTEC), Noordwijkerhout, The Netherlands, April 1984. Danner, D. J.; Brignaz, P. J.; Arceneaux, D., Jr.; Patel, V. Arch. Biochem. Biophys. 1973,156, 759-763. Forsyth, W. G. C.; Quensel, V. C.; Roberts, J. B. Biochim. Biophys. Acta 1960, 37, 322-326. Forsyth, W. G. C.; Quensel, V. C. Biochim. Biophys. Acta 1957,25, 155-160. Brown, B. R. “Oxidative Coupling of Phenols”; Taylor, W. I., Battersby, A.R., Eds.; Edward Dekker: New York, 1967; pp 167-201. Westerfield, W. W.; Lowe, C. J. Biol. Chem. 1942, 145, 463-470. Scott, A. I. “Oxidative Coupling of Phenols”; Taylor, W. I., Battersby, A. R., Eds.; Edward Dekker: New York, 1967; pp 95-117.
zyme. The application of 10 units/L HRP was sufficient to remove 95% of the 2,4-DCP at the concentration of 600 pg/L. This result cannot be generalized to all aromatic compounds. There appear to be several products of HRP reactions, depending on the substrate. These include polyphenols with carbon-carbon bonds on an aromatic ring, chlorinated furans, and dioxins. The products, rate, and extent of the reaction may be related to chlorine (or other functional group) substitution on the ring. Chlorine substitution appears to inhibit the reaction and favor the formation of dioxins and chlorinated furans, This illustrates the need to identify the products of an enzyme reaction when it is being applied to water treatment. The products of the enzymatic coupling are dependent on the substrate substituent groups. In drinking water treatment, operators have only limited control over raw water quality. Since chlorinated phenols may be partially transformed into dioxins and chlorinated furans, further research is required to evaluate the risk, if any, that this process presents in its application to potable water treatment. Registry No. 2-CP, 95-57-8; 2,4-DCP, 120-83-2;PCP, 87-86-5; HRP, 9003-99-0; hydrogen peroxide, 7722-84-1.
Literature Cited (1) Klibanov, A. M.; Alberti, E.; Morris, D.; Felshin, L. M. J.
Appl. Biochem. 1980,2,414-421. (2) Alberti, B. N.; Klibanov, A. M. Proc. Biotechnol. Bioeng. Symp. 1981,11, 373-379. (3) Klibanov, A. M.; Morris, E. D. Enzyme Microbiol. Technol. 1981,3, 119-122. (4) Schwartz, R. D. Hutchinson, D. B. Enzyme Microbiol. Technol. 1981,3, 361-367.
Received for review September 21, 1984. Revised manuscript received September 9, 1985. Accepted October 21, 1985.
PCBs Have Declined More Than DDT-Group Residues in Arctic Ringed Seals (Phoca hispida) between 1972 and 1981 Richard F. Addison* and Maurice E. Zinck Department of Fisheries and Oceans, Marine Ecology Laboratory, Bedford Institute of Oceanography, Dartmouth, N.S., Canada B2Y 4A2
Thomas G. Smith Arctic Biological Station, Ste. Anne de Bellevue, P.Q., Canada H9X 3R4
Mean DDT-group concentrations in the blubber of western Arctic ringed seals (Phoca hispida) sampled in 1981were less than 1pg-g-l wet weight blubber, and mean PCB concentrations were less than 2 pg-g-’ wet weight. Male seals had higher concentrations than did females. PCB concentrations were about half of those in a sample of the same population taken in 1972, when allowance was made for the variation of residue concentrations with age, sex, and condition. This decline probably results from the ban on PCB manufacture and use imposed in the early 1970s. Concentrations of DDT-group residues did not show any clear decline over the same interval, and the relative proportions of p,p’-DDT and p , p ’-DDE suggested that there is a continuing supply of DDT to the western Arctic. The most probable source of this is by atmospheric or water transport from the Far East, where DDT was used until at least the late 1970s.
Introduction Concentrations of organochlorine residues in seal blubber vary with the animal’s age, sex, and condition. In 0013-936X/86/0920-0253$01.50/0
males, residue concentrations in blubber tend to increase with age (1-4)) and a similar trend is seen in other marine mammals ( 5 , 6 ) . This probably occurs because the males have no route other than slow metabolic degradation by which to excrete these compounds. In female seals, residue concentrations appear not to increase with age ( 2 , 3 )or at least not as sharply as in males ( 4 ) . We have attributed this difference (7) to the females’ ability to “excrete” large amounts of lipid (e.g., 8) and its associated residue burden during lactation; some residues may also be transferred to the fetus during its development (9). In both males and females, residue concentrations are inversely related to blubber thickness (2,4);presumably, this reflects preferential deposition or catabolism of lipid relative to that of organochlorines. To detect trends in residue concentrations in seals that may indicate changes in environmental contamination by organochlorines,we must eliminate these natural variables. We can do this most simply by analyzing reproducing females, in which residue concentrations are virtually independent of age. Also, since lactating females secrete a
Published 1986 by the American Chemical Society
Environ. Sci. Technol., Vol. 20, No. 3, 1986
253
Table I. Comparison of Mean Ages, Lipid Contents, Blubber Thickness (BT), and Organochlorine Residue Concentrations in Male and Female Holman Island Ringed Seals Sampled in 1972 and 1981, Showing Probability ( P ) That Differences Over This Interval Are Significant by t Testa
females variable age, years lipid, % wet wt BT, em P,P’-DDE, wg g-’ wet wt P~P’-DDT,wg g-’ wet wt ZDDT, wg g-’ wet wt. PCB hg g-’ wet. wt. DDE % CDDT
1972 10.94 f 8.94 (9) 95.63 f 2.31 (9) 3.59 f 0.52 (8) 0.28 f 0.095 (9)
males P
1981 9.60 f 7.23 97.21 f 3.43 4.55 f 0.73 0.14 f 0.10
(15) (15) (15) (15)
NSb NS XO.01
