Enhanced Removal of Chlorophene and 17β-estradiol by Mn(III) in a Mixture Solution with Humic Acid: Investigation of Reaction Kinetics and Formation of Co-oligomerization Products

Reaction with soluble Mn(II) has been considered as a main decay pathway for superoxide in natural waters, accompanied by an important Mn redox cycling. In this study, the interaction of Mn(II) and humic acid (HA) was investigated in visible light irradiated water. Our results indicate that HA may play a dual role to act as a photosensitizer to produce superoxide anions (O₂^-) and as a strong ligand to stabilize the Mn(III), forming soluble Mn(III)_L species for substrate transformation. Furthermore, the reaction kinetics, products, and mechanisms of chlorophene (CP) and estradiol (E2) mixture in the Mn(II)/HA/visible light reaction systems were assessed. The removal of CP and E2 was enhanced by 24.3% and 13.2%, respectively, in mixture solution at initial concentration of 1.0 μM for each target contaminant, as compared to the case of single-compound degradation. Product identification and density functional theory calculations indicated that cross-coupling reaction of CP and E2 radicals was more likely to occur than the self-coupling reaction in mixture solution. In addition, estrogenic activities of initial reaction solution were also effectively decreased during the transformation process. These findings provide new insights into Mn(III)-mediated reactions to better understand the environmental fate of organic contaminant mixture in waters.