New insight into wastewater treatment by activation of sulfite with humic acid under visible light irradiation

Sulfite (S(IV)), as an alternative to persulfate, has demonstrated its cost-effectiveness and environmentally friendly nature, garnering increasing attention in Advanced Oxidation Processes (AOPs). Dissolved organic matter (DOM) commonly occurred in diverse environments and was often regarded as an interfering factor in sulfite-based AOPs. However, less attention has been paid to the promotion of the activation of sulfite by excited DOM, which could produce various reactive intermediates. The study focused on the activation of sulfite using visible light (VL) - excited humic acid (HA) to efficiently degrade many common organic pollutants, which was better than peroxydisulfate (PDS) and peroxymonosulfate (PMS) systems. Quenching experiments and electron paramagnetic resonance (EPR) analysis revealed that the triplet states of HA (3HA*) activated sulfite through energy transfer, resulting in the production of SO4•−, O2•−, and 1O2. The most significant active species found in the degradation of roxarsone (ROX) was 1O2, which was a non-radical pathway and exhibits high selectivity for pollutant degradation. This non-radical pathway was not commonly observed in traditional sulfite-based AOPs. Additionally, the coexistence of various inorganic anions, such as NO3−, Cl−, SO42−, CO32−, and PO43−, had little effect on the degradation of ROX. Furthermore, DOM from different natural water demonstrated efficient activation of S(IV) under light conditions, opening up new possibilities for applying sulfite-based advanced oxidation to the remediation of organic pollution in diverse sites and water bodies. In summary, this research offered promising insights into the potential application of sulfite-based AOPs, facilitated by photo-excited HA, as a new strategy for efficiently degrading organic pollutants in various environmental settings.