The overlooked role of UV185 induced high-energy excited states in the dephosphorization of organophosphorus pesticide by VUV/persulfate.

Vacuum ultraviolet (VUV) based advanced oxidation processes (AOPs) recently attracted widespread interests. However, the role of UV 185 in VUV is only considered to be generating a series of active species, while the effect of photoexcitation has long been overlooked. In this work, the role of UV 185 induced high-energy excited state for the dephosphorization of organophosphorus pesticides was studied using malathion as a model. Results showed malathion degradation was highly related to radical yield, while its dephosphorization was not. It was UV 185 rather than UV 254 or radical yield that was responsible for malathion dephosphorization by VUV/persulfate. DFT calculation results demonstrated that the polarity of P-S bond was further increased during UV 185 excitation, favoring dephosphorization while UV 254 did not. The conclusion was further supported by degradation path identification. Moreover, despite the fact that anions (Cl-, SO 4 2- and NO 3 -) considerably affected radical yield, only Cl- and NO 3 - with high molar extinction coefficient at 185 nm significantly affected dephosphorization. This study shed light on the crucial role of excited states in VUV based AOPs and provided a new idea for the development of mineralization technology of organophosphorus pesticides. [Display omitted] • High-energy excited states rather than radical yield dominated OPs mineralization. • Photoexcitation altered the regioselectivity of radical attack. • UV 185 weakened P–S bond, which decided dephosphorization, while UV 254 cannot. • Anions affected mineralization via UV 185 absorption rather than radical quenching. [ABSTRACT FROM AUTHOR]