Polychlorinated biphenyls (PCBs) were continuously receiving attention after their ban for use and production, owing to significant persistence, transport, and toxicity at trace level. Due to the field data gap of all 209 PCB congeners in previous studies, the source and environmental migration of lacustrine PCBs were not comprehensively understood. In this study, 209 PCB congeners in 277 water and 155 sediment samples collected from China’s 23 large lakes across a longitudinal transect (18–45 °N) were analyzed. Results showed that the concentrations of Σ209PCBs were 0.03–41.04 ng/L and 0.26–163.82 ng/g dry weight in lake water and sediment, respectively. In lake water, the dominant PCB congeners, detected in over 50% of all samples, were PCB 11, PCB 28+31, PCB 41+64+68, PCB 47+48+75, and PCB 51, with contributions to Σ209PCBs as 39.8%, 6.6%, 3.5%, 18.4%, and 6.4%, respectively. Source apportionment revealed that major contributions of PCB 11, 41+64+68, 47+48+75, 51, and 209, were mainly from unintentionally produced PCBs (UP-PCBs) while PCB 28+31 and the other congeners from historical PCB commercials. Therefore, the selective congener analysis (excluding UP-PCBs) common in previous lake studies was an omission. Simultaneously, the longitudinal fractionation of PCBs was also found in lake waters, likely caused by the East Asian monsoon. Moreover, fugacity fractions of PCBs between water and sediment indicated their overall equilibrium or net sorption. Overall, PCB 28+31 can be well indicative of PCB migration. This study provides basic information for the migration and transformation of trace toxic persistent organic pollutants.
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