Interactions of fluoroquinolone antibiotics with sodium hypochlorite in bromide-containing synthetic water: Reaction kinetics and transformation pathways

Seven popular fluoroquinolone antibiotics (FQs) in synthetic marine aquaculture water were subject to sodium hypochlorite (NaClO) disinfection scenario to investigate their reaction kinetics and transformation during chlorination. Reactivity of each FQ to NaClO was following the order of ofloxacin (OFL) > enrofloxacin (ENR) > lomefloxacin (LOM) > ciprofloxacin (CIP) ~ norfloxacin (NOR) >> pipemedic acid (PIP), while flumequine did not exhibit reactivity. The coexisting chlorine ions and sulfate ions in the water slightly facilitated the oxidation of FQs by NaClO, while humic acid was inhibitable to their degradation. The bromide ions promoted degradation of CIP and LOM, but restrained oxidation of OFL and ENR. By analysis of liquid chromatography with tandem mass spectrometry (LC-MS/MS), eight kinds of emerging brominated disinfection byproducts (Br-DBPs) caused by FQ_S were primarily identified in the chlorinated synthetic marine culture water. Through density functional theory calculation, the highest-occupied molecular orbital (HOMO) and the lowest-unoccupied molecular orbital (LUMO) characteristic as well as the charge distribution of the FQs were obtained to clarify transformation mechanisms. Their formation involved decarboxylation, ring-opening/closure, dealkylation and halogenation. Chlorine substitution occurred on the ortho-position of FQs's N4 and bromine substitution occurred on C8 position. The piperazine ring containing tertiary amine was comparatively stable, while this moiety with a secondary amine structure would break down during chlorination. Additionally, logK_ow and logBAF of transformation products were calculated by EPI-Suite^TM to analyze their bioaccumulation. The values indicated that Br-DBPs are easier to accumulate in the aquatic organism relative to their chloro-analogues and parent compounds.     

含溴黄浦江水消毒过程中溴代三卤甲烷和卤乙酸的生成特性

通过水厂出水DBPs调查和氯化培养实验探讨了黄浦江水中溴离子（Br-）在消毒过程中的迁移及对含溴副产物（溴代三卤甲烷和卤乙酸）生成的影响.结果表明,采用氯胺消毒的水厂出水中约10%的Br-迁移至Br-THMs和Br-HAAs.氯化培养时,在余氯充足的前提下增加Br-浓度,总有机溴（TOBr）和含溴副产物均增加.延长氯化...