Theoretical study on the OH-initiated oxidation mechanism of polyfluorinated dibenzo-p-dioxins under the atmospheric conditions.

Abstract

Density functional theory (DFT) calculations at the B3LYP/6-311++G(2df,p) level of theory have been carried out to investigate the atmospheric oxidation mechanisms of some polyfluorinated dibenzo-p-dioxins (PFDDs), initiated by OH radical. The computed results show that all OH addition reactions of PFDDs are thermodynamically spontaneous processes and the branch ratio of the PFDD-OH adducts is determined by the magnitude of the Gibbs free energies of activation (Δ(r)G(≠)) and hence rate constants (k) for addition reactions. The OH reactions with all studied PFDDs are dominated by Cγ-addition and the total rate constants for OH addition decrease with increasing the number of fluorine atom substituting at α positions. Under the atmospheric conditions, the subsequent O2 addition reactions of PFDD-OH adducts occur hardly thermodynamically and are slow kinetically. For PFDD-α(β)-OH adducts without F atom at same positions the main reaction pathway is H abstraction by O2, while PFDD-γ-OH adducts will undergo fused-ring C-O bond cleavage, affording the substituted phenoxy radicals.