Levels and Enantiomeric Signatures of Methyl Sulfonyl PCB and DDE Metabolites in Livers of Harbor Porpoises (Phocoena phocoena) from the Southern North Sea
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The concentration of 26 methyl sulfonyl metabolites ofpolychlorinated biphenyls (MeSO2-PCBs) and of p,p'-DDE(MeSO2-DDE) were determined in 19 liver samples from harborporpoises (Phocoena phocoena) stranded between 1997and 2000 on the Belgian and French North Sea Coasts. Thetotal concentration of MeSO2-PCBs ranged from 39 to4221 ng/g lipid weight (lw) and were generally higher inadults (age >2 yr, range 969-4 221 ng/g lw) than in juveniles(age <2 yr, range 39-1815 ng/g lw). The concentrationsof MeSO2-DDE were generally also higher in adults (21-96 ng/g lw) than in juveniles (0.5-60 ng/g lw). Congeners 3-and 4-MeSO2-CB101 were the dominating metabolites inall samples. Due to their preferential retention in the liver,the MeSO2-PCB congeners could be divided into twogroups. 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-chlorinesubstitution in the phenyl ring containing the methylsulfonyl group. The second group was dominated by the4-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 betweenindividual subjects and ranged from 15 to 419 and from 17to 1088, respectively. The ratio between the precursorPCB congeners and their corresponding metabolites rangedfrom 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 outof the 19 subjects. High enantiomeric excess (EF > 0.73or EF < 0.23) for the measured chiral MeSO2-PCB congenerswas found in all samples. This result may suggest thatone atropisomer may be preferentially formed in harborporpoises or that the atropisomers are retained in a highlyselective manner.

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