Effect of permanganate oxidation on the photoreactivity of dissolved organic matter for photodegradation of typical pharmaceuticals.

Permanganate has been widely used in the remediation of contaminated water due to its relatively strong oxidation properties and ease of use. The ubiquitous dissolved organic matter (DOM) in natural waters causes a significant sink of permanganate in treatments, which further impacts the photoformation of reactive species and the removal of trace pollutants by DOM. Significantly, the effect of permanganate oxidation on the photoreactivity of DOM remains unknown. The present paper investigated for the first time the photophysical and photochemical properties variation of DOM from different sources after permanganate oxidation. Results showed that the permanganate oxidation caused a decrease in UV absorbance, fluorescence intensity, aromaticity, and molecular weight for all tested DOM samples, as well as photoformation rate of DOM triplet states (DOM), singlet oxygen (O), and hydroxyl radical (OH) under simulated sunlight. Quantum yield of O showed positively linear correlations with both triplet quantum yield coefficient (f) and E2/E3 (ratio of absorbance at 254 and 365 nm) for all the DOM samples before and after permanganate oxidation. The quantum yield of OH exhibited no significant correlation with f or E2/E3. Permanganate oxidation inhibited the DOM-photosensitized indirect photodegradation of pollutants that do not absorb sunlight (e.g., decreased by 15-29%). For the tested pollutants that undergo direct photolysis under sunlight, their photodegradation was promoted (e.g., increased by 1-19%) in the permanganate oxidized DOM solutions due to the decrease of light-screening effect by DOM. These findings suggest that permanganate oxidation affects the photoreactivity of DOM and the corresponding photochemical fate of organic pollutants in natural waters.