Mechanism and kinetic properties of OH-initiated atmospheric oxidation degradation of methamidophos in the presence of O2/NO

Methamidophos is a member of the organophosphorus insecticides. In the present work, the mechanism of the OH radical-initiated atmospheric oxidation degradation of methamidophos and the possible degradation products were investigated with the aid of quantum chemical calculations. The geometrical parameters and vibrational frequencies were calculated at the MPWB1K/6-31+G(d,p) level. The energies of all the stationary points were carried out at the MPWB1K/6-311+G(3df,2p) level of theory. The rate constants of key elementary steps involved in the OH radical-initiated atmospheric degradation of methamidophos were calculated by meaning of the canonical variation transition-state (CVT) theory with the small curvature tunneling (SCT) correction over the possible atmospheric temperature range of 273-333 K. The rate-temperature formulas were fitted for the first time. The pre-exponential factor and the activation energy were obtained. Studies show that the OH additions from the trans-positions of the NH2 and OCH3 groups, the H abstractions from the SCH3 and OCH3 groups as well as the substitution reaction resulting in the products of CH3OP(O)OHNH2 and SCH3 are thermodynamically favorable reaction pathways for the reaction of methamidophos with OH radicals due to the low barrier and strong exothermicity. (C) 2016 Elsevier B.V. All rights reserved.