Photosensitized Transformation of Peroxymonosulfate in Dissolved Organic Matter Solutions under Simulated Solar Irradiation

Sulfate radical (SO₄^•-)-mediated advanced oxidation processes via peroxymonosulfate (PMS) activation have been extensively investigated. However, the phototransformation of PMS in sunlit dissolved organic matter (DOM) solution has not been previously examined. For the first time, the photosensitized transformation of PMS in DOM-enriched solutions under simulated solar irradiation was observed. The generation of reactive species, including ¹O₂, SO₄^•-, and ^•OH, was confirmed by electron paramagnetic resonance and quantified by chemical probes. SO₄^•- was the primary reactive species generated via the reaction of excited triplet DOM (³DOM*) with PMS. ³DOM* acted as a reactive reductant and was quickly oxidized by PMS, with an estimated reaction rate constant of (4.09 ± 0.21) × 10⁸ M^-1 s^-1. Compared to ³DOM*, one-electron-reducing DOM (DOM^•-) was a minor contributor to the photosensitized transformation of PMS, and the contribution of DOM^•- relied on the phenolic constituents. In addition, a series of different types of DOM, including terrestrial DOM, autochthonous DOM, and effluent organic matter and its fractions, were employed to examine the photosensitized transformation kinetics of PMS. Overall, the photosensitized transformation of PMS by irradiated DOM could be a useful and economical approach to generate SO₄^•- under environmentally relevant conditions.