The synergistic effect of radical and non-radical processes on the dephosphorization of dimethoate by vacuum ultraviolet: The overlooked roles of singlet oxygen atom and high-energy excited state

Organophosphorus pesticides are extensively utilized worldwide, but their incomplete dephosphorization poses significant environmental risks. This study investigates the dephosphorization of dimethoate (DMT), a representative organophosphorus pesticide, using a vacuum ultraviolet system. Surprisingly, in addition to hydroxyl radicals ( • OH), non-radical processes such as photoexcitation and singlet oxygen atoms (O( 1 D)) exert more significant effects on DMT dephosphorization. The degradation kinetics of DMT demonstrate a perfect linear correlation with the radical yield in both UV-based and VUV-based advanced oxidation processes (AOPs), with greater efficacy of radical attack observed in the VUV system. This heightened efficiency is attributed to the excitation of DMT to a high-energy excited state induced by UV 185 radiation. Additionally, • OH alone is inadequate for achieving complete dephosphorization of DMT. The Fukui index and singly occupied orbital (SOMO) analysis reveal that the O( 1 D) generated by UV 185 -induced photolysis of O 2 exhibits exceptional selectivity towards P=S bonds, thereby playing an indispensable role in the dephosphorization process of DMT. This study highlights the significant contribution of non-radical pathways in DMT dephosphorization by VUV, which holds great implications for the advancement of photochemical-based AOPs.