Insight into enhanced activation of permanganate under simulated solar irradiation: Rapid formation of manganese species

Herein, permanganate [Mn(VII)] was activated by simulated solar (SS) (SS/Mn(VII)), resulting in rapid degradation of micropollutants in several minutes, with rates of target micropollutants outnumbered those in the Mn(VII) alone and SS. To explore the mechanism in this process, 4-cholorphenol (4-CP), p-hydroxybenzoic acid (p-HBA), and enrofloxacin (ENR) were selected as model compounds. Lines of evidence indicated that reactive manganese species (RMnS) (i.e., Mn(III) and Mn(V)) rather than radicals from Mn(VII) photolysis participated in the conversion of model compounds. Interestingly, roles of RMnS differed among three model compounds, suggesting their selectivity toward micropollutants. Increasing Mn(VII) dosage proved greater micropollutant degradation, while impacts of pH on SS/Mn(VII) performance varied among model compounds. P-HBA and ENR showed the lowest degradation efficiency at alkaline, whereas 4-CP demonstrated the best performance at alkaline, indicating the reactivity of RMnS varied toward micropollutants at different pH values. The quantum yield of Mn(VII) was 8.36 ± 0.03 X 10-6 mol Einstein-1 at pH 7.0. Effects of common co-existing constituents (Cl-, HCO3-, and humic acid (HA)) on micropollutant degradation by SS/Mn(VII) were examined. Specifically, HCO3- positively influenced the 4-CP and p-HBA degradation, whereas ENR was not affected, likely owing to the selectivity of RMnS-HCO3- complexes. HA was conducive to degrade p-HBA due to the production of RMnS-HA complexes, but unfavorable for ENR and 4-CP degradation because of the competitive light absorption and Mn(VII). Furthermore, a number of degradation products of 4-CP, p-HBA, and ENR were identified and possible pathways were proposed accordingly. The effectiveness of this process for micropollutant degradation in real waters, natural sunlight, ultraviolet and visible light via cut-off filtering SS emission was confirmed. This work revealed a great potential of applying SS/Mn(VII) for the marked degradation of micropollutants and facilitated the understandings of Mn(III)/Mn(V) behaviors.