Atmospheric oxidation mechansim of polychlorinated biphenyls (PCBs) initiated by OH radicals

Long-range atmospheric transport (LRAT) is the main route for circulating polychlorinated biphenyls (PCBs) from sources to sinks. In the atmosphere, PCBs containing six and less chlorine substitutions exist mainly as vapour, which can be oxidized by OH radical. Here, using quantum chemistry and transition state theory, we calculated the rate coefficients for reactions of OH radical with selected PCBs. The predicted rate coefficients agree with the available experimental values within a factor of 3. Calculations show that all PCBs considered here are persistent with their half-lives longer than 24 h. Reactions of PCBs with OH radical start with OH addition to the phenyl rings, forming PCB-n-OH adducts. Fate of biphenyl-n-OH (BP-n-OH, n = 2, 3, 4) adducts in the atmosphere is investigated. Calculations show that these radical adducts react similarly to benzene-OH adducts, forming hydroxybiphenyl (HO-BP) as main product and bicyclic radicals as minor products in their reaction with O₂. Effective rates of reaction with O₂ in the atmosphere are relatively slow, ∼1400, ∼45000, and ∼800 s^-1 for BP-2-OH, BP-3-OH, and BP-4-OH, respectively. This suggests considerable reactions between BP-n-OH adducts and NO₂, forming nitrobiphenyls. The bicyclic radicals from BP-n-OH + O₂ would further transform to highly oxidized products as observed in a previous study. PCB-OH adducts react similarly as BP-n-OH radicals. For the three PCB-OH radicals considered here, their reactions with O₂ also form HO-PCBs and bicyclic radicals.