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Trophic transfer of polychlorinated biphenyl (PCB) congeners in zebra mussels (Dreissena polymorpha), round gobies (Neogobius melanstomus), and smallmouth bass (Micropterus dolomieu) were assessed in four sites along the south shore of the west and central basin of Lake Erie (all sites were in OH, USA). Total PCB levels in smallmouth bass (1,091-1,520 ng/g wet weight) and round gobies (118-256 ng/g wet weight) were similar among sites despite a west-to-east decrease in total PCB concentrations in zebra mussels (29-97 ng/g wet weight). At all sites, PCB body burden increased three- to fivefold at each successive trophic level, suggesting biomagnification in this nonnative food chain. Whereas fish species were dominated by the hexachlorine homologue, zebra mussels were dominated by penta- and hexachlorine homologues; the average degree of chlorination of PCBs was 56.1% for zebra mussels, 60.4% for round goby, and 59.9% for smallmouth bass bodies. Predictive structure-activity relationships based on chemical characteristics, such as the octanol-water partition coefficient (log K(ow)), had little predictive power on bioaccumulation and biotransformation of PCB congeners because of nonlinearity, threshold relationships, and species-specific differences. Calculated trophic transfer for the smallmouth bass-round goby linkage was higher than for the round goby-zebra mussel linkage. Only when PCB congeners were grouped by chemical structure first (vicinal [adjacent] H-atom position in the phenyl ring) were linear relationships achieved. It appeared that the chemical group to which each congener belonged influenced biotransformation more than species-specific (round gobies vs smallmouth bass) differences. Biotic changes at midtrophic levels, such as exotic species invasions, may have an increasingly important role in determining pollutant cycling and hence pollutant residues in top predators.