Mechanism of unactivated peroxymonosulfate-induced degradation of methyl parathion: Kinetics and transformation pathway

Abstract

Although various activated peroxymonosulfate (PMS) processes have been applied widely for the destruction of recalcitrant organics due to its high generation potential of various electrophiles reactive oxygen species (e.g., sulfate and hydroxyl radicals and singlet oxygen), non-radical-based PMS reactions with pollutants are poorly understood. Especially, relatively little information exists on the reactivity of PMS towards organic ester compounds such an organophosphorus pesticides (OPPs). Herein, we systematically studied the unactivated PMS-induced transformation of methyl parathion, a stubborn and toxic OPP. Specifically, direct reaction rather than electrophile radical-based oxidation was responsible for the rapid degradation of methyl parathion. The contribution of the produced singlet oxygen (¹O₂) from the self-decomposition of PMS to methyl parathion degradation can be neglected. The degradation rate constant (k_obs) was strongly dependent on PMS loading and solution pH. The implication of the PMS reaction with methyl parathion for environment treatment was further evaluated by investigating the effects of common water matrices such as sediment humic acids, Cl^-, and natural water. The identified metabolic products revealed that exposure to PMS resulted in hydrolysis and oxidation to methyl parathion. Further study demonstrated that PMS was also capable of effectively oxidizing other typical OPPs without explicit activation. This study provides novel insights into the reaction of methyl parathion with PMS, which indicate feasibility for the decontamination of OPP-contaminated environments.

Keywords: Degradation mechanism; Methyl parathion; Non-radical reaction; Peroxymonosulfate.