title: Mechanism and kinetics study on the OH-initiated oxidation of organophosphorus pesticide trichlorfon in atmosphere.
abstract: Trichlorfon [O,O-dimethyl-(2,2,2-trichloro-1-hydroxy-ethyl) phosphonate] (TCF) is a kind of widely used organophosphorus pesticides. In this paper, the mechanism and possible oxidation products for the OH-initiated reactions of TCF are studied at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p) level. The study shows that H abstraction reaction from the CH(3) group and the CH group as well as OH addition reaction to the P atom are energetically favorable for the reactions of TCF and the main products are (CH(3)O)(2)POOH (P1), CCl(3)CHOHPOOH(OCH(3)) (P2), CH(3)OPO(2) (P3), CCl(3)COPO(OCH(3))(2) (P6) and HCHO. On the basis of the quantum chemical information, the kinetic calculation is performed and the rate constants are calculated over a temperature range of 200-800K using the transition state theory and canonical variational transition state theory with small-curvature tunneling effect. The Arrhenius formulas of rate constants with the temperature are fitted and the lifetimes of the reaction species in the troposphere are estimated according to the rate constants, which can provide helpful information for the model simulation study.
authors.affiliation: Environment Research Institute, Shandong University, Jinan 250100, PR China.
authors.forename: Yuan
authors.initials: Y
authors.lastname: Bao
authors.forename: Chenxi
authors.initials: C
authors.lastname: Zhang
authors.forename: Wenbo
authors.initials: W
authors.lastname: Yang
authors.forename: Jingtian
authors.initials: J
authors.lastname: Hu
authors.forename: Xiaomin
authors.initials: X
authors.lastname: Sun
mesh_terms: D001272:Atmosphere / Q000737:chemistry; D004785:Environmental Pollutants / Q000737:chemistry*; D006878:Hydroxides / Q000737:chemistry; D007306:Insecticides / Q000737:chemistry*; D009569:Nitric Oxide / Q000737:chemistry; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry; D014236:Trichlorfon / Q000737:chemistry*
chemical_list: D004785:Environmental Pollutants; D006878:Hydroxides; D007306:Insecticides; D009569:Nitric Oxide; C031356:hydroxide ion; D014236:Trichlorfon; D010100:Oxygen