Cu(II) assisted peroxymonosulfate oxidation of sulfonamide antibiotics: The involvement of Cu(III)

Abstract

Cu(II) is generally considered to be a poor activator for PMS decomposition, thus the potential impact of trace Cu(II) on PMS induced oxidation of typical pollutants is always overlooked. In this study, we reported that trace Cu(II) could significantly promote PMS induced degradation of four selected sulfonamide antibiotics (SAs), namely, sulfamehoxazole (SMX), sulfathiazole (STZ), sulfamerazine (SMZ), and sulfamonomethoxine (SMM). Different from conventional PMS-induced oxidation process, high-valent Cu(III) was ascertained as the primary reactive intermediate for SAs degradation, which was confirmed by raman tests and electron paramagnetic resonance (EPR). High concentrations of Cu(II) or PMS were beneficial to degradation of the selected contaminants. In PMS/Cu(II) oxidation system, all the selected SAs could undergo several different degradation pathways including continuous oxidation of aniline group, hydroxylation and S–N bond cleavage. In particular, for six-membered SAs, such as SMZ and SMM, a SO2 extrusion pathway was also detected. The potential mechanism for Cu(III) formation was also proposed, which was believed to be highly related to the nature of the SAs. Hydroxylamine-SAs (N4–OH–SAs), generated from direct PMS oxidation of SAs, was deduced as the “promoter” for the whole oxidation process. And the generation of Cu(III) was likely to proceed through the interaction between PMS and Cu(I), which possibly derived from the reduction of Cu(II) by N4–OH–SAs. The results obtained in this study validated the contribution of Cu(III) to the elimination of pollutants and expanded our understanding of the oxidation process of PMS in the presence of trace amounts of Cu(II).