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 chlo...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 log BAF 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.展开更多
基金supported by the National Natural Science Foundation of China(No.51668005)the Open fund of Guangxi Key Laboratory of Clean Pulp&Papermaking and Pollution Control(No.KF201719)+3 种基金the Innovation Project of Guangxi-Graduate Education(No.YCSW2019029)the Natural Science Foundation of Guangxi Province(No.2020GXNSFAA159135)the Ba Gui Scholars Program Foundation(2014)supported by the State Key Laboratory for Conservation and Utilization of Subtropical Agro-Bioresources。
文摘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 log BAF 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.
