The theoretical investigation of OH-induced degradation mechanisms of isoproturon.

Ren, Xiaohua; Liu, Ruilong; Zhang, Shanshan; Zhang, Jinying

Herbicides are widely applied in agriculture, which causes emerging concern for contaminating surface water and groundwater. The degradation of isoproturon, being a typical phenylurea herbicide, has been studied much with advanced oxidation processes. However, little information on the detailed degradation mechanism from the theoretical level is available. In the present work, the degradation mechanisms of OH-initiated reactions of isoproturon were studied at the MPWB1K/6-311+G(3df, 2p)//MPWB1K/6-31+G(d, p) level. The calculation results display that H-atom abstraction, ·OH addition, and ·OH substitution pathways are found for ·OH and isoproturon reactions. For H-atom abstractions, the results show that aliphatic H atoms are more easily abstracted by ·OH than the aromatic H atoms, and the pathway R6 has the lowest energy barrier of 6.65 kcal mol-1, indicating that H in the -CH3 group attached to the N2 atom could be most favorably abstracted. Six pathways for ·OH addition to the six sites of the phenyl ring are identified with low energy barriers, which are in good accordance with the fact that the additions of ·OH to the phenyl ring were the important steps from experimental results. For ·OH substitution reactions, two pathways with high activation energies are found, and the corresponding products have been also detected from previous experimental studies, suggesting that the substitution reactions could also occur.