Promoted micropollutant degradation and structural evolution of natural organic matter by a novel S(IV)-based water treatment strategy

The ubiquity of various organic micropollutants in global water and wastewater has raised considerable concern about their cost-efficient elimination. This study reported that the novel UV365/FeTiOX/S(IV) system could accomplish superior abatement of different micropollutants (e.g., carbamazepine, CMZ) in 30–45 min with excellent reusability and stability of FeTiOX. In addition, this system functioned effectively to remove roxarsone and As(III)/As(V) by catalytic oxidation and adsorption, respectively. Mechanistic investigations suggested the dual roles of S(IV) in enhancing pollutant oxidation, i.e., promoted Fe(II)/Fe(III) cycle and photocatalysis. These processes facilitated the continuous generation of multiple oxidizing intermediates (e.g., hydroxyl radicals, sulfate radicals, and singlet oxygen), in which the last one was first proposed as the main contributor in iron-mediated S(IV)-based oxidation processes. Based on the product identification, the transformation pathways of four different micropollutants were tentatively unraveled. The in silico prediction suggested the lower environmental risks of the final reaction products than the precursors. Particularly, the structural alteration of humic acid was analyzed, indicating an increased O/C ratio after oxidative treatment. Overall, this study has implications for developing an efficient oxidation technique for removing multiple micropollutants in water and facilitating the mechanistic reactivity modulation of the S(IV)-based oxidation strategies in water treatment.