冀西北典型北方小城镇污水处理厂中抗生素的分布和去除
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摘要
抗生素在环境中作为一种新型污染物,是目前污水处理厂中重要的污染物之一.为考察小城镇污水处理厂对抗生素的去除效果,选择3种典型小城镇污水处理工艺(CASS、A~2/O及Orbal氧化沟工艺),研究了4种四环素类、3种β-内酰胺类、4种大环内酯类、3种喹诺酮类和2种磺胺类在进出水中的浓度分布、去除情况以及不同工艺抗生素去除效率,并对抗生素浓度与水质常规指标的相关性进行分析.结果表明,所研究的污水处理厂中氧氟沙星和诺氟沙星为主要抗生素,并且去除效果较好.5个污水处理厂运行情况良好,CASS工艺和Orbal氧化沟工艺对大部分抗生素的去除效果比A~2/O工艺好,抗生素去除率均能达到60%以上.同时,发现CASS工艺和A~2/O工艺对β-内酰胺类(氨苄西林、青霉素)、喹诺酮类(恩诺沙星、氧氟沙星和诺氟沙星)和大环内酯类(克拉霉素)的去除效果最好,Orbal氧化沟工艺对四环素类(四环素、土霉素)和磺胺类(磺胺嘧啶)的去除效果最好.将抗生素浓度和水质基本参数(NH_4~+-N、TN、COD、pH等)进行相关性分析后,发现抗生素浓度与水质基本参数NH_4~+-N、COD呈一定正相关,污染物浓度越高,红霉素(EM)、罗红霉素(ROX)、差向四环素盐酸盐(ETC)、克拉霉素(CLR)、环丙沙星(CIP)、氧氟沙星(OFX)、差向土霉素(E-OTC)、四环素(TC)、土霉素(OTC)以及诺氟沙星(NOR)的浓度也相对更高,这为确保小城镇污水厂的稳定运行,降低抗生素类污染物的生态风险提供了重要参考.
As a new,persistent pollutant in the environment,antibiotics are one of the most important pollutants in sewage treatment plants.The objective of this work was to investigate the concentration distribution and removal efficiency of antibiotics for three typical wastewater treatment technologies applied in small towns(CASS,A~2/O,and Orbal oxidation ditch) using solid phase extraction-liquid chromatography-tandem mass spectrometry.Sixteen typical antibiotics,including four tetracyclines,three β-lactams,four macrolides,three quinolones,and two sulfonamides,were analyzed in the influent and effluent.In addition,the relationship between the presence of antibiotics and the basic water quality(NH_4~+-N,TN,COD,pH,etc.) in the WWTPs was analyzed.The results showed that ofloxacin(OFX) and norfloxacin(NOR) were the main antibiotics in the WWTPs in this study.However,the concentrations of these two antibiotics in the effluent were low,indicating effective antibiotic removal efficiency.The antibiotic removal efficiency was higher than 60% in five of the WWTPs.Compared with the A~2/O process,the CASS and Orbal oxidation ditch technologies resulted in higher removals of most of the antibiotics.In addition,the CASS and A~2/O processes worked best for the removal of β-lactam [ampicillin(AMP) and penicillin(PCN) ],quinolones(ENR,NOR,and OFX),and macrolide(CLR),while the Orbal oxidation ditch worked best for the removal of tetracyclines(TC and OTC) and sulfonamides [sulfadiazine(SD) ].The correlation between antibioticconcentration and the basic parameters of water quality(NH_4~+-N,TN,COD,pH,etc.) was analyzed,and it was found that the water quality parameters had some effect on the concentration of antibiotics.With higher concentrations of the basic water quality parameters,higher the concentration of erythromycin(EM),roxithromycin(ROX),4-epi-Tetracycline(E-TC),clarithromycin(CLR),ciprofloxacin(CIP),ofloxacin(OFX),epioxytetracycline(E-OTC),tetracyclines(TC),oxytetracycline(OTC),and norfloxacin(NOR) were observed.In summary,it is important to ensure the stable operation of small town WWTPs to reduce the ecological risk of antibiotics.
As a new,persistent pollutant in the environment,antibiotics are one of the most important pollutants in sewage treatment plants.The objective of this work was to investigate the concentration distribution and removal efficiency of antibiotics for three typical wastewater treatment technologies applied in small towns(CASS,A~2/O,and Orbal oxidation ditch) using solid phase extraction-liquid chromatography-tandem mass spectrometry.Sixteen typical antibiotics,including four tetracyclines,three β-lactams,four macrolides,three quinolones,and two sulfonamides,were analyzed in the influent and effluent.In addition,the relationship between the presence of antibiotics and the basic water quality(NH_4~+-N,TN,COD,pH,etc.) in the WWTPs was analyzed.The results showed that ofloxacin(OFX) and norfloxacin(NOR) were the main antibiotics in the WWTPs in this study.However,the concentrations of these two antibiotics in the effluent were low,indicating effective antibiotic removal efficiency.The antibiotic removal efficiency was higher than 60% in five of the WWTPs.Compared with the A~2/O process,the CASS and Orbal oxidation ditch technologies resulted in higher removals of most of the antibiotics.In addition,the CASS and A~2/O processes worked best for the removal of β-lactam [ampicillin(AMP) and penicillin(PCN) ],quinolones(ENR,NOR,and OFX),and macrolide(CLR),while the Orbal oxidation ditch worked best for the removal of tetracyclines(TC and OTC) and sulfonamides [sulfadiazine(SD) ].The correlation between antibioticconcentration and the basic parameters of water quality(NH_4~+-N,TN,COD,pH,etc.) was analyzed,and it was found that the water quality parameters had some effect on the concentration of antibiotics.With higher concentrations of the basic water quality parameters,higher the concentration of erythromycin(EM),roxithromycin(ROX),4-epi-Tetracycline(E-TC),clarithromycin(CLR),ciprofloxacin(CIP),ofloxacin(OFX),epioxytetracycline(E-OTC),tetracyclines(TC),oxytetracycline(OTC),and norfloxacin(NOR) were observed.In summary,it is important to ensure the stable operation of small town WWTPs to reduce the ecological risk of antibiotics.
引文
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[10]Xuan W,Quan C,Shuyi L.An optimal water allocation model based on water resources security assessment and its application in Zhangjiakou Region,northern China[J].Resources,Conservation and Recycling,2012,69:57-65.
[11]Chen H,Liu S,Xu X R,et al.Antibiotics in the coastal environment of the Hailing Bay region,South China Sea:spatial distribution,source analysis and ecological risks[J].Marine Pollution Bulletin,2015,95(1):365-373.
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[15]柴玉峰,冯玉启,张玉秀,等.猪场废水中24种抗生素同时检测方法优化[J].环境化学,2017,36(10):2147-2154.Chai Y F,Feng Y Q,Zhang Y X,et al.Optimization of an analytical method for the simultaneous determination of 24antibiotics in swine wastewater[J].Environmental Chemistry,2017,36(10):2147-2154.
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[18]洪蕾洁,石璐,张亚雷,等.固相萃取-高效液相色谱法同时测定水体中的10种磺胺类抗生素[J].环境科学,2012,33(2):652-657.Hong L J,Shi L,Zhang Y L,et al.Simultaneous determination of 10 sulfonamide antibiotics in water by solid-phase extraction and high performance liquid chromatography[J].Environmental Science,2012,33(2):652-657.
[19]He K,Soares A D,Adejumo H,et al.Detection of a wide variety of human and veterinary fluoroquinolone antibiotics in municipal wastewater and wastewater-impacted surface water[J].Journal of Pharmaceutical and Biomedical Analysis,2015,106:136-143.
[20]Zhang Q H,Yang W N,Ngo H H,et al.Current status of urban wastewater treatment plants in China[J].Environment International,2016,92-93:11-22.
[21]甘秀梅,严清,高旭,等.典型抗生素在中国西南地区某污水处理厂中的行为和归趋[J].环境科学,2014,35(5):1817-1823.Gan X M,Yan Q,Gao X,et al.Occurrence and fate of typical antibiotics in a wastewater treatment plant in Southwest China[J].Environmental Science,2014,35(5):1817-1823.
[22]Guo X Y,Feng C H,Zhang J H,et al.Role of dams in the phase transfer of antibiotics in an urban river receiving wastewater treatment plant effluent[J].Science of the Total Environment,2017,607-608:1173-1179.
[23]Yan C X,Yang Y,Zhou J L,et al.Antibiotics in the surface water of the Yangtze Estuary:occurrence,distribution and risk assessment[J].Environmental Pollution,2013,175:22-29.
[24]Leung H W,Minh T B,Murphy M B,et al.Distribution,fate and risk assessment of antibiotics in sewage treatment plants in Hong Kong,South China[J].Environment International,2012,42:1-9.
[25]张琦,叶能胜,谷学新,等.β-内酰胺类抗生素分析检测技术及其应用研究进展[J].化学通报,2009,72(5):394-400.Zhang Q,Ye N S,Gu X X,et al.Development and application of analytical methods for analyses ofβ-lactam antibiotics residues[J].Chemistry,2009,72(5):394-400.
[26]Lu M Q,Niu X J,Chen W Y,et al.Phosphine production in anaerobic wastewater treatment under tetracycline antibiotic pressure[J].Journal of Environmental Sciences,2017,doi:10.1016/j.jes.2017.10.018.(in press)
[27]Yuan X J,Qiang Z M,Ben W W,et al.Distribution,mass load and environmental impact of multiple-class pharmaceuticals in conventional and upgraded municipal wastewater treatment plants in East China[J].Environmental Science:Processes&Impacts,2015,17(3):596-605.
[28]Li B,Zhang T,Xu Z Y,et al.Rapid analysis of 21 antibiotics of multiple classes in municipal wastewater using ultra performance liquid chromatography-tandem mass spectrometry[J].Analytica Chimica Acta,2009,645(1-2):64-72.
[29]Li B,Zhang T.Mass flows and removal of antibiotics in two municipal wastewater treatment plants[J].Chemosphere,2011,83(9):1284-1289.
[30]Kovalova L,Siegrist H,Singer H,et al.Hospital wastewater treatment by membrane bioreactor:performance and efficiency for organic micropollutant elimination[J].Environmental Science&Technology,2012,46(3):1536-1545.
[31]Wang M Y,Shen W T,Yan L,et al.Stepwise impact of urban wastewater treatment on the bacterial community structure,antibiotic contents,and prevalence of antimicrobial resistance[J].Environmental Pollution,2017,231:1578-1585.
[32]Le-Minh N,Khan S J,Drewes J E,et al.Fate of antibiotics during municipal water recycling treatment processes[J].Water Research,2010,44(15):4295-4323.
[2]Golet E M,Strehler A,Alder A C,et al.Determination of fluoroquinolone antibacterial agents in sewage sludge and sludgetreated soil using accelerated solvent extraction followed by solidphase extraction[J].Analytical Chemistry,2002,74(21):5455-5462.
[3]Du J,Geng J J,Ren H Q,et al.Variation of antibiotic resistance genes in municipal wastewater treatment plant with A2O-MBR system[J].Environmental Science and Pollution Research,2015,22(5):3715-3726.
[4]谯华,蒋国正,方振东,等.小城镇污水一体化生物处理工艺技术研究进展[J].四川环境,2017,36(4):158-162.Qiao H,Jiang G Z,Fang Z D,et al.Research progress of integrated biological wastewater treatment technology for small towns[J].Sichuan Environment,2017,36(4):158-162.
[5]Ahmed M J.Adsorption of quinolone,tetracycline,and penicillin antibiotics from aqueous solution using activated carbons:review[J].Environmental Toxicology and Pharmacology,2017,50:1-10.
[6]Tran N H,Chen H J,Reinhard M,et al.Occurrence and removal of multiple classes of antibiotics and antimicrobial agents in biological wastewater treatment processes[J].Water Research,2016,104:461-472.
[7]Zheng J,Su C,Zhou J W,et al.Effects and mechanisms of ultraviolet,chlorination,and ozone disinfection on antibiotic resistance genes in secondary effluents of municipal wastewater treatment plants[J].Chemical Engineering Journal,2017,317:309-316.
[8]郑春燕,王艳华,李树苑,等.四种小城镇污水处理工艺投资分析与探讨[J].中国给水排水,2014,30(12):63-67.Zheng C Y,Wang Y H,Li S Y,et al.Analysis and discussion on investments of four sewage treatment technologies in small towns[J].China Water&Wastewater,2014,30(12):63-67.
[9]Michael I,Rizzo L,Mc Ardell C S,et al.Urban wastewater treatment plants as hotspots for the release of antibiotics in the environment:a review[J].Water Research,2013,47(3):957-995.
[10]Xuan W,Quan C,Shuyi L.An optimal water allocation model based on water resources security assessment and its application in Zhangjiakou Region,northern China[J].Resources,Conservation and Recycling,2012,69:57-65.
[11]Chen H,Liu S,Xu X R,et al.Antibiotics in the coastal environment of the Hailing Bay region,South China Sea:spatial distribution,source analysis and ecological risks[J].Marine Pollution Bulletin,2015,95(1):365-373.
[12]Jrgensen S E,Halling-Srensen B.Drugs in the environment[J].Chemosphere,2000,40(7):691-699.
[13]Díaz-Cruz M S,López de Alda M J,BarcelóD.Environmental behavior and analysis of veterinary and human drugs in soils,sediments and sludge[J].Tr AC Trends in Analytical Chemistry,2003,22(6):340-351.
[14]Zhang R J,Tang J H,Li J,et al.Occurrence and risks of antibiotics in the coastal aquatic environment of the Yellow Sea,North China[J].Science of the Total Environment,2013,450-451:197-204.
[15]柴玉峰,冯玉启,张玉秀,等.猪场废水中24种抗生素同时检测方法优化[J].环境化学,2017,36(10):2147-2154.Chai Y F,Feng Y Q,Zhang Y X,et al.Optimization of an analytical method for the simultaneous determination of 24antibiotics in swine wastewater[J].Environmental Chemistry,2017,36(10):2147-2154.
[16]国家环境保护总局.水和废水监测分析方法[M].(第四版).北京:中国环境科学出版社,2002.
[17]March-RossellóG A.Rapid methods for detection of bacterial resistance to antibiotics[J].Enfermedades Infecciosas y Microbiologia Clinica,2017,35(3):182-188.
[18]洪蕾洁,石璐,张亚雷,等.固相萃取-高效液相色谱法同时测定水体中的10种磺胺类抗生素[J].环境科学,2012,33(2):652-657.Hong L J,Shi L,Zhang Y L,et al.Simultaneous determination of 10 sulfonamide antibiotics in water by solid-phase extraction and high performance liquid chromatography[J].Environmental Science,2012,33(2):652-657.
[19]He K,Soares A D,Adejumo H,et al.Detection of a wide variety of human and veterinary fluoroquinolone antibiotics in municipal wastewater and wastewater-impacted surface water[J].Journal of Pharmaceutical and Biomedical Analysis,2015,106:136-143.
[20]Zhang Q H,Yang W N,Ngo H H,et al.Current status of urban wastewater treatment plants in China[J].Environment International,2016,92-93:11-22.
[21]甘秀梅,严清,高旭,等.典型抗生素在中国西南地区某污水处理厂中的行为和归趋[J].环境科学,2014,35(5):1817-1823.Gan X M,Yan Q,Gao X,et al.Occurrence and fate of typical antibiotics in a wastewater treatment plant in Southwest China[J].Environmental Science,2014,35(5):1817-1823.
[22]Guo X Y,Feng C H,Zhang J H,et al.Role of dams in the phase transfer of antibiotics in an urban river receiving wastewater treatment plant effluent[J].Science of the Total Environment,2017,607-608:1173-1179.
[23]Yan C X,Yang Y,Zhou J L,et al.Antibiotics in the surface water of the Yangtze Estuary:occurrence,distribution and risk assessment[J].Environmental Pollution,2013,175:22-29.
[24]Leung H W,Minh T B,Murphy M B,et al.Distribution,fate and risk assessment of antibiotics in sewage treatment plants in Hong Kong,South China[J].Environment International,2012,42:1-9.
[25]张琦,叶能胜,谷学新,等.β-内酰胺类抗生素分析检测技术及其应用研究进展[J].化学通报,2009,72(5):394-400.Zhang Q,Ye N S,Gu X X,et al.Development and application of analytical methods for analyses ofβ-lactam antibiotics residues[J].Chemistry,2009,72(5):394-400.
[26]Lu M Q,Niu X J,Chen W Y,et al.Phosphine production in anaerobic wastewater treatment under tetracycline antibiotic pressure[J].Journal of Environmental Sciences,2017,doi:10.1016/j.jes.2017.10.018.(in press)
[27]Yuan X J,Qiang Z M,Ben W W,et al.Distribution,mass load and environmental impact of multiple-class pharmaceuticals in conventional and upgraded municipal wastewater treatment plants in East China[J].Environmental Science:Processes&Impacts,2015,17(3):596-605.
[28]Li B,Zhang T,Xu Z Y,et al.Rapid analysis of 21 antibiotics of multiple classes in municipal wastewater using ultra performance liquid chromatography-tandem mass spectrometry[J].Analytica Chimica Acta,2009,645(1-2):64-72.
[29]Li B,Zhang T.Mass flows and removal of antibiotics in two municipal wastewater treatment plants[J].Chemosphere,2011,83(9):1284-1289.
[30]Kovalova L,Siegrist H,Singer H,et al.Hospital wastewater treatment by membrane bioreactor:performance and efficiency for organic micropollutant elimination[J].Environmental Science&Technology,2012,46(3):1536-1545.
[31]Wang M Y,Shen W T,Yan L,et al.Stepwise impact of urban wastewater treatment on the bacterial community structure,antibiotic contents,and prevalence of antimicrobial resistance[J].Environmental Pollution,2017,231:1578-1585.
[32]Le-Minh N,Khan S J,Drewes J E,et al.Fate of antibiotics during municipal water recycling treatment processes[J].Water Research,2010,44(15):4295-4323.