Chlorinated biphenyl methylsulfones and biphenylols were determined in samples of human milk from Canadian donors. Fifty samples containing an average of 10.8 ng g(-1) (w/w) of total PCBs were found to contain an average of 68 Pg g(-1) of chlorinated biphenyl methylsulfone. The major congeners were 3-methylsulfonyl-2,2',4',5,5'-pentachlorobiphenyl. 4-methylsulfonyl-2,2',3',4',5,-pentachlorobiphenyl and 4-methylsulfonyl-2,2',3',5,5',6'-hexachlorobiphenyl. Twelve of these samples were analyzed for five chlorinated biphenylols and the 4-methoxy-2,2',3,4',5,5',6-heptachlorobiphenylol congener was detected in all at an average concentration of 1.9 pg g(-1). The chlorinated biphenylols appear to be minor residual metabolites in human milk from the general population. The fifty samples with an average of 8.4 ng g(-1) of p,p'-DDE also contained an-average of 16.5 pg g(-1) of the corresponding methylsulfone. Both the total PCB methylsulfone and p,p' DDE methylsulfone were correlated with total PCB and p,p' DDE contents, respectively. Copyright (C) 1996 Elsevier Science Ltd