Levels and enantiomeric signatures of methyl sulfonyl PCB and DDE metabolites in livers of harbor porpoises (Phocoena phocoena) from the southern North Sea
[en] The concentration of 26 methyl sulfonyl metabolites of polychlorinated biphenyls (MeSO2-PCBs) and of p,p'-DDE (MeSO2-DDE) were determined in 19 liver samples from harbor porpoises (Phocoena phocoena) stranded between 1997 and 2000 on the Belgian and French North Sea Coasts. The total concentration of MeSO2-PCBs ranged from 39 to 4221 ng/g lipid weight (lw) and were generally higher in adults (age >2 yr, range 969-4221 ng/g lw) than in juveniles (age <2 yr, range 39-1815 ng/g lw). The concentrations of MeSO2-DDE were generally also higher in adults (2196 ng/g lw) than in juveniles (0.5-60 ng/g lw). Congeners 3- and 4-MeSO2-CB101 were the dominating metabolites in all samples. Due to their preferential retention in the liver, the MeSO2-PCB congeners could be divided into two groups. The first group was dominated by the 3-MeSO2-PCB congeners and consisted of MeSO2-CB31, -CB49, -CB52, -CB87, and -CB101, which all have a 2,5-chlorine substitution in the phenyl ring containing the methyl sulfonyl group. The second group was dominated by the 4-MeSO2-PCB congeners and consisted of MeSO2-CB64, -CB91, -CB110, and -CB132, which all have a 2,3,6-chlorine substitution. The ratios of sum of PCBs/sum of MeSO2-PCBs and p,p-DDE/MeSO2-DDE differed greatly between individual subjects and ranged from 15 to 419 and from 17 to 1088, respectively. The ratio between the precursor PCB congeners and their corresponding metabolites ranged from 0.6 (CB49) to 175 (CB174). Enantiomeric fractions (EFs) for MeSO2-PCB atropisomers, which include 3-MeSO2-CB132, 3-MeSO2-CB149, 4-MeSO2-CB149, 3-MeSO2-CB174, and 4-MeSO2-CB174, were also measured in 8 out of the 19 subjects. High enantiomeric excess (EF > 0.73 or EF < 0.23) for the measured chiral MeSO2-PCB congeners was found in all samples. This result may suggest that one atropisomer may be preferentially formed in harbor porpoises or that the atropisomers are retained in a highly selective manner.
Research Center/Unit :
MARE - Centre Interfacultaire de Recherches en Océanologie - ULiège
Chu, Shaogang; Universiteit Antwerpen - UA > Toxicological Center
Covaci, Adrian; Universiteit Antwerpen - UA > Toxicological Center
Haraguchi, Koichi; Daiichi College of Pharmaceutical Sciences
Voorspoels, Stefan; Universiteit Antwerpen - UA > Toxicological Center
Van de Vijver, Kristin Inneke; Universiteit Antwerpen - UA > Department of Biology
Das, Krishna ; Université de Liège - ULiège > Département des sciences et gestion de l'environnement > Océanologie
Bouquegneau, Jean-Marie ; Université de Liège - ULiège > Département des sciences et gestion de l'environnement > Océanologie - Doyen de la Faculté des Sciences
Levels and enantiomeric signatures of methyl sulfonyl PCB and DDE metabolites in livers of harbor porpoises (Phocoena phocoena) from the southern North Sea
Publication date :
15 October 2003
Journal title :
Environmental Science and Technology
ISSN :
0013-936X
eISSN :
1520-5851
Publisher :
Amer Chemical Soc, Washington, United States - Washington
Letcher, R. J.; Klasson-Wehler, E.; Bergman, Å. Methyl sulfone and hydroxylated metabolites of polychlorinated biphenyls. In The Handbook of Environmental Chemistry, New Types of Persistent Halogenated Compounds; Paasivirta, J., Ed.; Springer-Verlag: Berlin, 2000; pp 315-360.
Larsen, G. L.; Bergman, Å.; Klasson-Wehler, E.; Bass, N. M. Chem. Biol. Interact. 1991, 77, 315-323.
Larsson, C. Atropisomers of PCB methyl sulfone metabolites: Radiosynthesis, analysis and distribution. Ph.D. Dissertation, University of Stockholm, Sweden, 2002.
Berggren, P.; Arrhenius, F. Sightings of Harbor Porpoises (Phocoena phocoena) in Swedish Waters before 1990; No. 99-107; Reports International Whaling Commission: 1995; p 16.
Covaci, A.; Van de Vijver, K.; De Coen, W.; Das, K.; Bouquegneau, J. M.; Blust, R.; Schepens, P. Mar. Pollut. Bull. 2002, 44, 1157-1165.
Haraguchi, K.; Kuroki, H.; Matsuda, Y. J. Agric. Food Chem. 1987, 35, 178-182.
Chu, S. G.; Covaci, A.; Haraguchi, K.; Schepens, P. Analyst 2002, 127, 1621-1626.
Troisi, G. M.; Haraguchi, K.; Simmonds, M. P.; Mason, C. F. Arch. Environ. Contam. Toxicol. 1998, 35, 121-128.
Boon, J. P.; Lewis, W. E.; Tjoen-A-Choy, M. R.; Allchin, C. R.; Law, R. J.; de Boer, J.; ten Hallers-Tjabbes, C. C.; Zegers, B. N. Environ. Sci. Technol. 2002, 36, 4025-4032.
Troisi, G. M.; Haraguchi, K.; Kaydoo, D. S.; Nyman, M.; Aguilar, A.; Borrell, A.; Siebert, U.; Mason, C. F. J. Toxicol. Environ. Health A 2000, 62, 1-8.
Letcher, R. J.; Norstrom, R. J.; Bergman, Å. Sci. Total Environ. 1995, 160/161, 409-420.
Chu, S. G.; Covaci, A.; Haraguchi, K.; Schepens, P. Environ. Health Perspect. 2003, 111, 1222-1227.
Boon, J. P.; Van Arnhem, E.; Jansen, S.; Kannan, N., Petrick, G.; Schulz, D.; Duinker, J. C.; Reijnders, P. J.; Goksoyr, A. The toxicokinetics of PCBs in marine mammals with special reference to possible interactions of individual congeners with the cytochrome P450-dependent monooxygenase system: an overview. In Persistent Pollutants in Marine Ecosystems; Walker, C. H., Livingstone, D. R., Eds.; Pergamon Press: Oxford, 1992; pp 119-160.
Tanabe, S.; Watanabe, S.; Kan, H.; Tatsukawa, R. Mar. Mamm. Sci. 1988, 4, 103-124.
Boon, J. P.; van der Meer, J.; Allchin, C. R.; Law, R. J.; Klungoye, J.; Leonard, P. E. G.; Spliid, H.; Storr-Hansen, E.; McKenzie, C.; Wells, D. Arch. Environ. Contam. Toxicol. 1997, 33, 298-311.
