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Comparison of chlorination behaviors between norfloxacin and ofloxacin: Reaction kinetics, oxidation products and reaction pathways

Wang, Xiaofeng, Li, Yin, Li, Ruiyang, Yang, Hongwei, Zhou, Beihai, Wang, Xiaomao, Xie, Yuefeng
Chemosphere 2019 v.215 pp. 124-132
Lewis acids, Lewis bases, benzene, chemical bonding, chlorination, chlorine, hydrolysis, liquid chromatography, moieties, nitrogen, norfloxacin, ofloxacin, oxidation, reaction kinetics, reducing agents, tandem mass spectrometry, water treatment, China
Fluoroquinolones (FQs) are very ubiquitous in water environment in China. The commonly application of free available chlorine (FAC) during water treatment stimulated the focus on the transformation of FQs during chlorination. Among these FQs, norfloxacin (NOR) and ofloxacin (OFL) are the representatives of secondary amine FQs and tertiary amine FQs, respectively. To better understand the difference between secondary amine FQs and tertiary amine FQs during chlorination, reaction kinetics, products and mechanisms were determined. The maximum kₐₚₚ of NOR were four orders of magnitude higher than that of OFL. Moreover, eleven products of NOR and twelve products of OFL were obtained by LC−MS/MS analysis. For the two FQs, the common reactive sites were three nitrogen atoms, benzene ring, carboxyl group and double bond by chlorination. For OFL, the ether ring was also active in aqueous system. The formation mechanisms of these products were presented in this study. The main reaction pathways were electrophilic addition to nitrogen, nucleophilic substitution to benzene ring, halodecarboxylation of carboxyl group and hydrolysis of ether ring. Na₂S₂O₃ as a reducing agent had large effect on the chlorination of secondary amine FQ, but no effect on tertiary amine FQ. Be different to secondary amine FQ, the opening of quinolone ring happened in tertiary amine FQ after halodecarboxylation of carboxyl group.