紫外/氯高级氧化降解典型抗生素磺胺二甲嘧啶的试验
|
摘要
以水体中存在的典型抗菌药磺胺二甲嘧啶(sulfamethazine,SMZ)为研究对象,基于紫外/氯(UV/氯)高级氧化方法,研究了SMZ的降解机制与转化路径。SMZ的降解符合拟一级反应动力学,其降解速率随SMZ初始浓度的升高而降低。采用Box-Behnken试验设计以及DOE响应分析,评估了SMZ降解的主要影响因素。结果表明,氯投加量是影响UV/氯降解SMZ速率的主控因素,其次为pH,二者的影响效应值分别为-22.82和12.06,其交互影响作用效应值仅为1.52,表明增加氯投加量或降低pH均对SMZ的降解有促进作用,但二者无明显相互促进或抑制的效果。质谱分析结果显示,SMZ降解过程产生了10种主要转化产物,基于前线轨道理论分析,明确了SMZ上的7号氮原子(N7)发生羟基和氯原子取代的反应路径,解析了取代产物的二次产物形成机制。
The degradation of sulfamethazine(SMZ), a typical antibiotic wildly existing in natural water, by UV/chlorine advanced oxidation process was studied. The degradation of SMZ followed the pseudo first-order kinetic model, and its degradation rate decreased with the increase of initial concentration of SMZ. Main factors contributing to the SMZ degradation were evaluated by Box-Behnken experimental design and DOE-response surface analysis. The results showed that chlorine dosage was the main effect affecting the degradation rate of SMZ by UV/chlorine, followed by pH. The effect values of chlorine and pH were-22.82 and 12.06, respectively. However, chlorine-pH interaction effect value was only 1.52, which indicated that increasing chlorine dosage or lowering pH value promoted the degradation of SMZ but neither has obvious synergistic or antagonistic effect. The results of mass spectrometry detection showed that 10 major products were formed in the degradation process of SMZ. According to the frontier orbital theory, the substitution reaction pathway of hydroxyl and chlorine atoms at N7 was observed in the oxidation and chlorine oxidation of SMZ. Mechanism of the formation of secondary products was explained.
The degradation of sulfamethazine(SMZ), a typical antibiotic wildly existing in natural water, by UV/chlorine advanced oxidation process was studied. The degradation of SMZ followed the pseudo first-order kinetic model, and its degradation rate decreased with the increase of initial concentration of SMZ. Main factors contributing to the SMZ degradation were evaluated by Box-Behnken experimental design and DOE-response surface analysis. The results showed that chlorine dosage was the main effect affecting the degradation rate of SMZ by UV/chlorine, followed by pH. The effect values of chlorine and pH were-22.82 and 12.06, respectively. However, chlorine-pH interaction effect value was only 1.52, which indicated that increasing chlorine dosage or lowering pH value promoted the degradation of SMZ but neither has obvious synergistic or antagonistic effect. The results of mass spectrometry detection showed that 10 major products were formed in the degradation process of SMZ. According to the frontier orbital theory, the substitution reaction pathway of hydroxyl and chlorine atoms at N7 was observed in the oxidation and chlorine oxidation of SMZ. Mechanism of the formation of secondary products was explained.
引文
[1] WEI R,GE F,HUANG S,et al.Occurrence of veterinary antibiotics in animal wastewater and surface water around farms in Jiangsu Province,China[J].Chemosphere,2011,82(10):1408-1414.
[2] BATT A L,BRUCE I B,AGA D S.Evaluating the vulnerability of surface waters to antibiotic contamination from varying wastewater treatment plant discharges[J].Environmental Pollution,2006(2):295-302.
[3] 姜蕾,蔡海芸,卢宁.黄浦江上游水体中抗生素的分布特征与生态风险[J].净水技术,2014,33(s2):81-85.
[4] 张孟丹,梁俊平,李芳芳,等.磺胺二甲嘧啶和恩诺沙星对鲤仔鱼的急性毒性试验[J].河南水产,2017(5):20-23.
[5] 刘丽丽,吕鹏,闫艳春.磺胺二甲嘧啶对斑马鱼胚胎的急性毒性作用[J].中国渔业质量与标准,2018,8(1):34-39.
[6] 常志强,李健,刘萍.磺胺二甲嘧啶的危害特征[J].中国渔业质量与标准,2012,2(4):15-20.
[7] YANG Y,SHI J,YANG Y,et al.Transformation of sulfamethazine during the chlorination disinfection process:Transformation,kinetics,and toxicology assessment[J].Journal of Environmental Sciences,2019(2):48-56.
[8] NASSAR R,RIFAI A,TRIVELLA A,et al.Aqueous chlorination of sulfamethazine and sulfamethoxypyridazine:Kinetics and transformation products identification[J].Journal of Mass Spectrometry,2018,53(7):614-623.
[9] NASSAR R,TRIVELLA A,MOKH S,et al.Photodegradation of sulfamethazine,sulfamethoxypiridazine,amitriptyline,and clomipramine drugs in aqueous media[J].Journal of Photochemistry & Photobiology:A Chemistry,2016,30(3):176-182.
[10] YI Z,WANG J,TANG Q,et al.Photolysis of sulfamethazine using UV irradiation in an aqueous medium[J].Rsc Advances,2018,8(3):1427-1435.
[11] XIANG Y,FANG J,SHANG C.Kinetics and pathways of ibuprofen degradation by the UV/chlorine advanced oxidation process[J].Water Research,2016,50(5):301-308.
[12] KONG X,JIANG J,MA J,et al.Degradation of atrazine by UV/chlorine:Efficiency,influencing factors,and products[J].Water Research,2016,50(5):15-23.
[13] 刘凡.真空紫外/氯技术处理水中磺胺二甲嘧啶的研究[D].北京:北京交通大学,2015.
[14] CHAMBERLAIN E,ADAMS C.Oxidation of sulfonamides,macrolides,and carbadox with free chlorine and monochloramine[J].Water Research,2006,40(13):2517-2526.
[15] MA G G,DíAZ-CRUZ M S,BARCELó D.Kinetic studies and characterization of photolytic products of sulfamethazine,sulfapyridine and their acetylated metabolites in water under simulated solar irradiation[J].Water Research,2012,46(3):711-722.
[16] WU Z,FANG J,XIANG Y,et al.Roles of reactive chlorine species in trimethoprim degradation in the UV/chlorine process:Kinetics and transformation pathways[J].Water Research,2016,50(21):272-282.
[17] CARPINTEIRO I,RODIL R,QUINTANA J B,et al.Reaction of diazepam and related benzodiazepines with chlorine:Kinetics,transformation products and in-silico toxicological assessment[J].Water Research,2017,51(17):280-289.
[18] KONG X,WU Z,REN Z,et al.Degradation of lipid regulators by the UV/chlorine process:Radical mechanisms,chlorine oxide radical (ClO·)-mediated transformation pathways and toxicity changes[J].Water Research,2018,52(12):242-250.
[19] WU Z,GUO K,FANG J,et al.Factors affecting the roles of reactive species in the degradation of micropollutants by the UV/chlorine process[J].Water Research,2017,51(23):351-360.
[20] GAFFNEY V D J,CARDOSO V V,BENOLIEL M J,et al.Chlorination and oxidation of sulfonamides by free chlorine:Identification and behaviour of reaction products by UPLC-MS/MS[J].Journal of Environmental Management,2016,44(2):466-477.
[21] GARCíA-GALáN M J,RODRíGUEZ-RODRíGUEZ C E,VICENT T,et al.Biodegradation of sulfamethazine by Trametes versicolor:Removal from sewage sludge and identification of intermediate products by UPLC-QqTOF-MS[J].Science of the Total Environment,2011,40(22):5505-5512.
[22] BARHOUMI N,OTURAN N,OLVERA-VARGAS H,et al.Pyrite as a sustainable catalyst in electro-Fenton process for improving oxidation of sulfamethazine:Kinetics,mechanism and toxicity assessment[J].Water Research,2016,50(9):52-61.
[23] FAN Y,JI Y,KONG D,et al.Kinetic and mechanistic investigations of the degradation of sulfamethazine in heat-activated persulfate oxidation process[J].Journal of Hazardous Materials,2015,41(24):39-47.
[24] ZHANG B,XIAN Q,GONG T,et al.DBPs formation and genotoxicity during chlorination of pyrimidines and purines bases[J].Chemical Engineering Journal,2017,22(1):884-890.
[25] QU R,XU B,MENG L,et al.Ozonation of indigo enhanced by carboxylated carbon nanotubes:Performance optimization,degradation products,reaction mechanism and toxicity evaluation[J].Water Research,2015,49(1):316-327.
[2] BATT A L,BRUCE I B,AGA D S.Evaluating the vulnerability of surface waters to antibiotic contamination from varying wastewater treatment plant discharges[J].Environmental Pollution,2006(2):295-302.
[3] 姜蕾,蔡海芸,卢宁.黄浦江上游水体中抗生素的分布特征与生态风险[J].净水技术,2014,33(s2):81-85.
[4] 张孟丹,梁俊平,李芳芳,等.磺胺二甲嘧啶和恩诺沙星对鲤仔鱼的急性毒性试验[J].河南水产,2017(5):20-23.
[5] 刘丽丽,吕鹏,闫艳春.磺胺二甲嘧啶对斑马鱼胚胎的急性毒性作用[J].中国渔业质量与标准,2018,8(1):34-39.
[6] 常志强,李健,刘萍.磺胺二甲嘧啶的危害特征[J].中国渔业质量与标准,2012,2(4):15-20.
[7] YANG Y,SHI J,YANG Y,et al.Transformation of sulfamethazine during the chlorination disinfection process:Transformation,kinetics,and toxicology assessment[J].Journal of Environmental Sciences,2019(2):48-56.
[8] NASSAR R,RIFAI A,TRIVELLA A,et al.Aqueous chlorination of sulfamethazine and sulfamethoxypyridazine:Kinetics and transformation products identification[J].Journal of Mass Spectrometry,2018,53(7):614-623.
[9] NASSAR R,TRIVELLA A,MOKH S,et al.Photodegradation of sulfamethazine,sulfamethoxypiridazine,amitriptyline,and clomipramine drugs in aqueous media[J].Journal of Photochemistry & Photobiology:A Chemistry,2016,30(3):176-182.
[10] YI Z,WANG J,TANG Q,et al.Photolysis of sulfamethazine using UV irradiation in an aqueous medium[J].Rsc Advances,2018,8(3):1427-1435.
[11] XIANG Y,FANG J,SHANG C.Kinetics and pathways of ibuprofen degradation by the UV/chlorine advanced oxidation process[J].Water Research,2016,50(5):301-308.
[12] KONG X,JIANG J,MA J,et al.Degradation of atrazine by UV/chlorine:Efficiency,influencing factors,and products[J].Water Research,2016,50(5):15-23.
[13] 刘凡.真空紫外/氯技术处理水中磺胺二甲嘧啶的研究[D].北京:北京交通大学,2015.
[14] CHAMBERLAIN E,ADAMS C.Oxidation of sulfonamides,macrolides,and carbadox with free chlorine and monochloramine[J].Water Research,2006,40(13):2517-2526.
[15] MA G G,DíAZ-CRUZ M S,BARCELó D.Kinetic studies and characterization of photolytic products of sulfamethazine,sulfapyridine and their acetylated metabolites in water under simulated solar irradiation[J].Water Research,2012,46(3):711-722.
[16] WU Z,FANG J,XIANG Y,et al.Roles of reactive chlorine species in trimethoprim degradation in the UV/chlorine process:Kinetics and transformation pathways[J].Water Research,2016,50(21):272-282.
[17] CARPINTEIRO I,RODIL R,QUINTANA J B,et al.Reaction of diazepam and related benzodiazepines with chlorine:Kinetics,transformation products and in-silico toxicological assessment[J].Water Research,2017,51(17):280-289.
[18] KONG X,WU Z,REN Z,et al.Degradation of lipid regulators by the UV/chlorine process:Radical mechanisms,chlorine oxide radical (ClO·)-mediated transformation pathways and toxicity changes[J].Water Research,2018,52(12):242-250.
[19] WU Z,GUO K,FANG J,et al.Factors affecting the roles of reactive species in the degradation of micropollutants by the UV/chlorine process[J].Water Research,2017,51(23):351-360.
[20] GAFFNEY V D J,CARDOSO V V,BENOLIEL M J,et al.Chlorination and oxidation of sulfonamides by free chlorine:Identification and behaviour of reaction products by UPLC-MS/MS[J].Journal of Environmental Management,2016,44(2):466-477.
[21] GARCíA-GALáN M J,RODRíGUEZ-RODRíGUEZ C E,VICENT T,et al.Biodegradation of sulfamethazine by Trametes versicolor:Removal from sewage sludge and identification of intermediate products by UPLC-QqTOF-MS[J].Science of the Total Environment,2011,40(22):5505-5512.
[22] BARHOUMI N,OTURAN N,OLVERA-VARGAS H,et al.Pyrite as a sustainable catalyst in electro-Fenton process for improving oxidation of sulfamethazine:Kinetics,mechanism and toxicity assessment[J].Water Research,2016,50(9):52-61.
[23] FAN Y,JI Y,KONG D,et al.Kinetic and mechanistic investigations of the degradation of sulfamethazine in heat-activated persulfate oxidation process[J].Journal of Hazardous Materials,2015,41(24):39-47.
[24] ZHANG B,XIAN Q,GONG T,et al.DBPs formation and genotoxicity during chlorination of pyrimidines and purines bases[J].Chemical Engineering Journal,2017,22(1):884-890.
[25] QU R,XU B,MENG L,et al.Ozonation of indigo enhanced by carboxylated carbon nanotubes:Performance optimization,degradation products,reaction mechanism and toxicity evaluation[J].Water Research,2015,49(1):316-327.
© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |