The multiple roles of phenols in the degradation of aniline contaminants by sulfate radicals: A combined study of DFT calculations and experiments

Recent research revealed inhibition or enhancement of dissolved organic matter (DOM) to the degradation of trace organic contaminants (TrOC) in natural and engineered water systems. Phenols containing acetyl, carboxyl, formyl, hydroxy, and methoxy groups were selected as the model DOM to quantitatively study their roles in the degradation of simple anilines, sulfonamide antibiotics, phenylurea pesticides by sulfate radicals (SO 4 • − ). Experimental results found that p -methoxyphenol inhibited aniline and sulfamethoxazole degradation by thermally activated peroxydisulfate (TAP), while p -acetylphenol slightly promoted aniline degradation. Quantum chemical calculations were applied to study the microscopic mechanism and kinetics of phenols affecting the degradation of aniline pollutants (AN) in three ways: competitively reacting with SO 4 • − , repairing aniline cationic radicals (AN • + ) and phenylaminyl radicals (AN(-H) • ), and generating phenoxy radicals to degrade anilines. Generally, the degradation of sulfonamides and phenylureas prefer to be inhibited by hydroxy- and methoxy-phenols with low oxidation potential ( E ox ), due to their diffusion-limiting reaction with SO 4 • − and rapid back-reduction AN • + with the calculated rate constants of (0.02 − 6.38) × 10 9 M −1 s −1 . Phenols repairing AN(-H) • through H abstraction reaction is speculated to possibly dominate the joint degradation of phenols and anilines by TAP, which has a poor correlation with E ox . This study provides mechanistic insight into the chemical behavior of complex and heterogeneous DOM in complex aqueous environments.