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Polychlorinated biphenyls (PCBs) are important environmental contaminants, and their toxicity to wildlife and humans are of major concern. PCBs form persistent and abundant metabolites, PCB methyl sulfones, that accumulate in biota. We now report that certain hydroxylated PCB metabolites show a strong and selective accumulation in mammalian blood. Plasma from experimentally PCB-dosed rats and blood from environmentally exposed grey seals (Halichoerus grypus) and humans were analyzed. Among all possible hydroxylated metabolites of PCB that may be formed, only a few, dominated by 4-OH-2,3,5,3',4'-pentachlorobiphenyl and 4-OH-2,3,5,6,2',4',5'-heptachlorobiphenyl, were found in the blood samples. All identified compounds have a structure with the hydroxy group in a para or meta position, with chlorine atoms on vicinal carbon atoms. The concentrations of hydroxylated PCB in the blood were almost in the same range as the most persistent PCB congeners both for seals and humans.