Transformation of antimicrobial agent sulfamethazine by peroxymonosulfate: Radical vs. nonradical mechanisms

Peroxymonosulfate (PMS) is increasingly used as an oxidant for in situ remediation of organic contaminants in soil and groundwater. In this study we demonstrated that sulfamethazine (SMZ) could be transformed by PMS in the absence of any activators. Such transformation was ascribed to the oxidation by PMS per se, rather than free radicals (SO₄^- or HO), superoxide (O₂^-), or singlet oxygen (¹O₂). The aniline moiety of SMZ molecule was the reactive site for PMS oxidation, leading to the formation of nitrated products. This nitration pathway in fact played a significant role in the removal of SMZ in activated PMS oxidation processes. For instance, it contributed 26% of the total SMZ transformation, while SO₄^- contributed the other 74% during the removal of SMZ, in Co(II)/PMS oxidation process with initial PMS and Co(II) concentrations of 1.0 mM and 0.1 μM, respectively. Similar nitration reaction also occurred to other sulfonamide antibiotics bearing an aniline moiety upon the reaction with PMS. Since nitrated sulfonamide antibiotics appear more persistent than the parent compounds and may cause other environmental problems, such a pathway should not be desired. Therefore, PMS might not be an ideal oxidant for the treatment of sulfonamide antibiotics and other compounds having aniline moieties, especially in subsurface remediation practices where efficient activation of PMS represents a major challenge.