Atmospheric oxidation mechanisms of polychlorinated dibenzo-p-dioxins are different from those of benzene and dibenzofuran: A theoretical prediction

The reaction mechanisms of dibenzo-p-dioxin (DD) and 2,3,7,8-TCDD with OH radical have been studied using density functional theory calculations. Under the atmospheric conditions, ca 42% of DD + OH reaction proceeds as formation of DD − OH-β adduct, which will react with O2 slowly; while the rest will proceed as formation of DD − OH-γ adduct, which will decompose to the substituted phenoxy radical P1 by the fused-ring C–O bond cleavage. For 2,3,7,8-TCDD + OH, the reaction will predominantly form the substituted phenoxy radical P2. The reaction mechanisms are drastically different from the peroxy mechanism for the atmospheric oxidations of benzene and dibenzofuran.