Experimental and theoretical study on Fe(VI) oxidative degradation of dichlorophen in water: Kinetics and reaction mechanisms.

Dichlorophenol (DCP), a commonly used fungicide and insecticide, is widely found in waters and wastewaters. Herein, the degradation of DCP by Ferrate (Fe(VI)) in different matrices was comprehensively investigated. In pure water, a complete removal of DCP was achieved in 300 s at [Fe(VI)]:[DCP] molar ratio of 2:1. The presence of HA (10 mg L) inhibited DCP degradation to a certain extent. A total of twenty degradation products were identified by HPLC/MS analysis. Based on these products, reaction pathways including the cleavage of C-C bridge bond, hydroxylation, and radical coupling were proposed. These reaction mechanisms were further rationalized by theoretical calculations. The analyses of Wiberg bond orders and transition state indicated that C-C bond was the most vulnerable site for cleavage, and C site was the most likely site for hydroxyl addition. Mulliken atomic spin densities distribution suggested that self-coupling products was easily generated via C-O-C coupling ways. Finally, the feasibility of applying Fe(VI) to degrade DCP (20 μM) in a municipal wastewater effluent and a lake water was evaluated and verified. The findings in this study are of relevance in designing Fe(VI)-based treatment strategy for chlorine-containing persistent pesticides.