Mechanism for OH-Initiated Degradation of 2,3,7,8-Tetrachlorinated Dibenzo-p-Dioxins in the Presence of O2 and NO/H2O

Abstract

The atmospheric oxidation of 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TeCDD) is investigated theoretically by high-accuracy molecular orbital calculation. The study shows that the OH radical can easily be added to the C atom adjacent to the O atom in dioxin ring to form OH radical adduct. The 2,3,7,8-TeCDD-OH adduct can immediately react with O(2) to form the 2,3,7,8-TeCDD-OH-O(2) adduct which can react with NO or H(2)O to complete the decomposition process. The degradation mechanism varies with the addition position of O(2) and the O-abstraction by NO. The OH radical can be reproduced through the H-abstraction of H(2)O and initiate a new round of degradation. The direct dynamic calculation is performed, and the rate constants is calculated over a temperature range of 200-1200 K, using the canonical variational transition state theory with small-curvature tunneling effect. The four-parameter formula of rate constants with the temperature is fitted and the lifetimes of the reaction species in the troposphere are estimated according to the rate constants, which is helpful for the atmospheric model study on the formation and degradation of dioxin.