Kinetics and mechanisms for sulfamethoxazole transformation in the phenolic acid-laccase (Trametes versicolor) system.

Abstract

Oxidation of phenolic acids (PCs) by laccase could produce various kinds of reactive oxygen species (ROS), which is expected to have substantial impact on the transformation of antibiotics like sulfamethoxazole (SMX) in soil and aquatic environments. In this study, the formation of semiquinones radical (SQ●-), superoxide anion radical (O2●-), hydrogen peroxide (H2O2), hydroxyl radical (●OH), and singlet oxygen (1O2) in a laccase-gallic acid (GA) reaction system was confirmed. Meanwhile, GA would be transformed to its monomeric quinone and quinones of di- and tri-polymers. Transformation of SMX by laccase alone is negligible, while which was greatly enhanced in the presence of GA at the optimal pH of 5.5. The dissolved O2 was the requisite for transformation of SMX due to its fundamental role in the formation of SQ●-, the key species initializing the chain reactions for the generation of other ROS. The quenching experiments indicated O2●- and 1O2 were the main ROS responsible for SMX transformation. A total of thirteen products were proposed for the SMX transformation, with the pathways including the breaking of S-N bond, the cleavage of oxazole ring, electrophilic substitution, Michael addition, and condensation reactions. Moreover, the existence of electron-withdrawing substitution group on the benzene ring of PCs and less stability of SQ●- was believed to be favorable for the transformation of SMX. The results above expand our understanding on the role of oxidation of PCs by laccase in the SMX transformation in environments and are of significance in relation to use of laccase in dealing with SMX pollution.