Inhibitory Effect of Dissolved Organic Matter on the Transformation of Selected Anilines and Sulfonamide Antibiotics Induced by the Sulfate Radical.

Dissolved organic matter (DOM) has been shown to inhibit the oxidation of aromatic amines initiated by excited triplet states, an effect that was attributed to the reduction of oxidation intermediates back to their parent compounds. The present study focuses on the quantification of an analogous inhibitory effect of DOM on aqueous oxidations induced by the sulfate radical (SO4·-). Second-order rate constants for the SO4·--induced transformation of selected anilines and sulfonamide antibiotics were determined by competition kinetics in the presence and absence of DOM from three different isolates at pH 8. In the presence of 1 mgC L-1 of DOM, a significant reduction in the rate constant was observed for most of the compounds compared to DOM-free solutions, but for two electron-rich anilines, increases in the rate constant were measured. For 4-cyanoaniline and sulfamethoxazole, the DOM concentration dependence of the rate constant consisted of a sharp decrease up to ∼1.0 mgC L-1 of DOM followed by a region of slight changes or even increases for higher DOM concentrations (up to 5 mgC L-1). This behavior was attributed to the occurrence of the aforementioned inhibitory effect and a counteracting accelerated transformation of the contaminants due to reactions with secondary radical oxidants resulting from DOM oxidation by SO4·-. Both effects of inhibition and secondary oxidants should be considered when assessing the abatement of aromatic amines in SO4·--based advanced oxidation processes.