4种磺胺类药物及乙酰化代谢物在污水处理厂的去除及机制
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摘要
乙酰化代谢物是磺胺类药物的重要代谢产物.为研究4种常见磺胺类药物及其乙酰化代谢物在污水厂中的去除机制,根据污水停留时间采集厦门某A2/O型工艺污水厂不同处理单元的污水和污泥样品,采用固相萃取-高效液相色谱串联质谱法检测目标化合物.结果显示,8种目标物中有6种在水体中被检测出,污泥中有5种目标物被检测出.计算总去除率及各个处理单元间的去除率,结果表明,磺胺二甲基嘧啶在污水厂中总去除率几乎为0,而其他5种化合物都有不同程度的去除,但不同目标物在各处理单元的去除率不同.利用质量平衡,分析各物质可能的去除机制,磺胺二甲基嘧啶可能去除机制为污泥吸附,磺胺嘧啶、磺胺甲基嘧啶和磺胺甲唑可能的去除机制均为生物降解.
Acetyl metabolites are the major metabolites of sulfonamides. In order to investigate the removal mechanism of four commonly used sulfonamides and their metabolites in wastewater treatment plants,sulfonamides and their corresponding acetyl metabolites in wastewater and sludge in a wastewater treatment plant equipped with A2/O in Xiamen City were sampled. Sample selection was based on the hydraulic retention time. Solid phase extraction followed by high performance liquid chromatography tandem mass spectrometry( HPLC-MS/MS) was applied to analyze the target compounds. Results showed that six out of eight of the target compounds were detected in the wastewater,while five were detected in the sludge. Based on the removal efficiencies overall and of the different compartments,the concentration of sulfamethazine was almost unchanged during wastewater treatment plant( WWTP)processes,the other sulfonamides were removed with different removal efficiencies. Removal efficiencies varied for every compartment.The potential removal pathways were analyzed based on the mass balance of the target compounds. The removal pathway of sulfamethazine was sludge adsorption,while the potential removal mechanism of sulfamerazine,sulfadiazine,and sulfamethoxazole was biodegradation.
Acetyl metabolites are the major metabolites of sulfonamides. In order to investigate the removal mechanism of four commonly used sulfonamides and their metabolites in wastewater treatment plants,sulfonamides and their corresponding acetyl metabolites in wastewater and sludge in a wastewater treatment plant equipped with A2/O in Xiamen City were sampled. Sample selection was based on the hydraulic retention time. Solid phase extraction followed by high performance liquid chromatography tandem mass spectrometry( HPLC-MS/MS) was applied to analyze the target compounds. Results showed that six out of eight of the target compounds were detected in the wastewater,while five were detected in the sludge. Based on the removal efficiencies overall and of the different compartments,the concentration of sulfamethazine was almost unchanged during wastewater treatment plant( WWTP)processes,the other sulfonamides were removed with different removal efficiencies. Removal efficiencies varied for every compartment.The potential removal pathways were analyzed based on the mass balance of the target compounds. The removal pathway of sulfamethazine was sludge adsorption,while the potential removal mechanism of sulfamerazine,sulfadiazine,and sulfamethoxazole was biodegradation.
引文
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[16]Li H,Sun H W,Zhang J X,et al.Highly sensitive and simultaneous determination of sixteen sulphonamide antibiotics,four acetyled metabolites and trimethoprim in meat by rapid resolution liquid chromatography-tandem mass spectrometry[J].Food Control,2013,31(2):359-365.
[17]Zhang Y,Zhou W E,Li S H,et al.A simple,accurate,timesaving and green method for the determination of 15 sulfonamides and metabolites in serum samples by ultra-high performance supercritical fluid chromatography[J].Journal of Chromatography A,2016,1432:132-139.
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[20]Yan Q,Gao X,Huang L,et al.Occurrence and fate of pharmaceutically active compounds in the largest municipal wastewater treatment plant in Southwest China:mass balance analysis and consumption back-calculated model[J].Chemosphere,2014,99:160-170.
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[22]G9bel A,Thomsen A,Mc Ardell C S,et al.Occurrence and sorption behavior of sulfonamides,macrolides,and trimethoprim in activated sludge treatment[J].Environmental Science&Technology,2005,39(11):3981-3989.
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[24]Yang S F,Lin C F,Lin A Y C,et al.Sorption and biodegradation of sulfonamide antibiotics by activated sludge:experimental assessment using batch data obtained under aerobic conditions[J].Water Research,2011,45(11):3389-3397.
[25]García Galán M J,Díaz-Cruz M S,BarcelóD.Removal of sulfonamide antibiotics upon conventional activated sludge and advanced membrane bioreactor treatment[J].Analytical and Bioanalytical Chemistry,2012,404(5):1505-1515.
[26]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.
[27]周海东,黄霞,文湘华.城市污水中有关新型微污染物PPCPs归趋研究的进展[J].环境工程学报,2007,1(12):1-9.Zhou H D,Huang X,Wen X H.Progress of the studies on occurrence and fate of new emerging micro-pollutants-PPCPs in municipal wastewaters[J].Chinese Journal of Environmental Engineering,2007,1(12):1-9.
[28]高俊红,王兆炜,张涵瑜,等.兰州市污水处理厂中典型抗生素的污染特征研究[J].环境科学学报,2016,36(10):3765-3773.Gao J H,Wang Z W,Zhang H Y,et al.Occurrence and the fate of typical antibiotics in sewage treatment plants in Lanzhou[J].Acta Scientiae Circumstantiae,2016,36(10):3765-3773.
[2]金磊,姜蕾,韩琪,等.华东地区某水源水中13种磺胺类抗生素的分布特征及人体健康风险评价[J].环境科学,2016,37(7):2515-2521.Jin L,Jiang L,Han Q,et al.Distribution characteristics and health risk assessment of thirteen sulfonamides antibiotics in a drinking water source in East China[J].Environmental Science,2016,37(7):2515-2521.
[3]Lertpaitoonpan W,Ong S K,Moorman T B.Effect of organic carbon and pH on soil sorption of sulfamethazine[J].Chemosphere,2009,76(4):558-564.
[4]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.
[5]柴玉峰,张玉秀,陈梅雪,等.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[J].环境科学,2018,39(6):2724-2731.Chai Y F,Zhang Y X,Chen M X,et al.Distribution and treatment of antibiotics in typical WWTPs in small towns in China[J].Environmental Science,2018,39(6):2724-2731.
[6]张晓娇,柏杨巍,张远,等.辽河流域地表水中典型抗生素污染特征及生态风险评估[J].环境科学,2017,38(11):4553-4561.Zhang X J,Bai Y W,Zhang Y,et al.Occurrence,distribution,and ecological risk of antibiotics in surface water in the Liaohe river basin,China[J].Environmental Science,2017,38(11):4553-4561.
[7]Hossain A,Nakamichi S,Habibullah-Al-Mamun M,et al.Occurrence and ecological risk of pharmaceuticals in river surface water of Bangladesh[J].Environmental Research,2018,165:258-266.
[8]Sun Q,Lv M,Hu A Y,et al.Seasonal variation in the occurrence and removal of pharmaceuticals and personal care products in a wastewater treatment plant in Xiamen,China[J].Journal of Hazardous Materials,2014,277:69-75.
[9]Martinez J L.Environmental pollution by antibiotics and by antibiotic resistance determinants[J].Environmental Pollution,2009,157(11):2893-2902.
[10]Xu J,Xu Y,Wang H M,et al.Occurrence of antibiotics and antibiotic resistance genes in a sewage treatment plant and its effluent-receiving river[J].Chemosphere,2015,119:1379-1385.
[11]Zonaras V,Tyrpenou A,Alexis M,et al.Determination of sulfadiazine,trimethoprim,and N4-acetyl-sulfadiazine in fish muscle plus skin by Liquid Chromatography-Mass Spectrometry.Withdrawal-time calculation after in-feed administration in gilthead sea bream(Sparus aurata L.)fed two different diets[J].Journal of Veterinary Pharmacology and Therapeutics,2016,39(5):504-513.
[12]Andriamalala A,Vieublé-Gonod L,Dumeny V,et al.Fate of sulfamethoxazole,its main metabolite N-ac-sulfamethoxazole and ciprofloxacin in agricultural soils amended or not by organic waste products[J].Chemosphere,2018,191:607-615.
[13]Kishida K,Furusawa N.Application of shielded column liquid chromatography for determination of sulfamonomethoxine,sulfadimethoxine,and their N4-acetyl metabolites in milk[J].Journal of Chromatography A,2004,1028(1):175-177.
[14]刘思思,杜鹃,陈景文,等.加速溶剂萃取-高效液相色谱-串联质谱联用测定莱州湾海水养殖区野生鱼肌肉中19种抗生素及2种磺胺代谢产物残留[J].色谱,2014,32(12):1320-1325.Liu S S,Du J,Chen J W,et al.Determination of 19 antibiotic and 2 sulfonamide metabolite residues in wild fish muscle in mariculture areas of Laizhou Bay using accelerated solvent extraction and high performance liquid chromatography-tandem mass spectrometry[J].Chinese Journal of Chromatography,2014,32(12):1320-1325.
[15]Meng Z,Shi Z H,Liang S X,et al.Residues investigation of fluoroquinolones and sulphonamides and their metabolites in bovine milk by quantification and confirmation using ultraperformance liquid chromatography-tandem mass spectrometry[J].Food Chemistry,2015,174:597-605.
[16]Li H,Sun H W,Zhang J X,et al.Highly sensitive and simultaneous determination of sixteen sulphonamide antibiotics,four acetyled metabolites and trimethoprim in meat by rapid resolution liquid chromatography-tandem mass spectrometry[J].Food Control,2013,31(2):359-365.
[17]Zhang Y,Zhou W E,Li S H,et al.A simple,accurate,timesaving and green method for the determination of 15 sulfonamides and metabolites in serum samples by ultra-high performance supercritical fluid chromatography[J].Journal of Chromatography A,2016,1432:132-139.
[18]Ashfaq M,Li Y,Wang Y W,et al.Occurrence,fate,and mass balance of different classes of pharmaceuticals and personal care products in an anaerobic-anoxic-oxic wastewater treatment plant in Xiamen,China[J].Water Research,2017,123:655-667.
[19]Petrie B,Mc Adam E J,Lester J N,et al.Obtaining process mass balances of pharmaceuticals and triclosan to determine their fate during wastewater treatment[J].Science of the Total Environment,2014,497-498:553-560.
[20]Yan Q,Gao X,Huang L,et al.Occurrence and fate of pharmaceutically active compounds in the largest municipal wastewater treatment plant in Southwest China:mass balance analysis and consumption back-calculated model[J].Chemosphere,2014,99:160-170.
[21]Li J N,Cheng W X,Xu L K,et al.Occurrence and removal of antibiotics and the corresponding resistance genes in wastewater treatment plants:effluents'influence to downstream water environment[J].Environmental Science and Pollution Research,2016,23(7):6826-6835.
[22]G9bel A,Thomsen A,Mc Ardell C S,et al.Occurrence and sorption behavior of sulfonamides,macrolides,and trimethoprim in activated sludge treatment[J].Environmental Science&Technology,2005,39(11):3981-3989.
[23]Huang Y J,Cheng M M,Li W H,et al.Simultaneous extraction of four classes of antibiotics in soil,manure and sewage sludge and analysis by liquid chromatography-tandem mass spectrometry with the isotope-labelled internal standard method[J].Analytical Methods,2013,5(15):3721-3731.
[24]Yang S F,Lin C F,Lin A Y C,et al.Sorption and biodegradation of sulfonamide antibiotics by activated sludge:experimental assessment using batch data obtained under aerobic conditions[J].Water Research,2011,45(11):3389-3397.
[25]García Galán M J,Díaz-Cruz M S,BarcelóD.Removal of sulfonamide antibiotics upon conventional activated sludge and advanced membrane bioreactor treatment[J].Analytical and Bioanalytical Chemistry,2012,404(5):1505-1515.
[26]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.
[27]周海东,黄霞,文湘华.城市污水中有关新型微污染物PPCPs归趋研究的进展[J].环境工程学报,2007,1(12):1-9.Zhou H D,Huang X,Wen X H.Progress of the studies on occurrence and fate of new emerging micro-pollutants-PPCPs in municipal wastewaters[J].Chinese Journal of Environmental Engineering,2007,1(12):1-9.
[28]高俊红,王兆炜,张涵瑜,等.兰州市污水处理厂中典型抗生素的污染特征研究[J].环境科学学报,2016,36(10):3765-3773.Gao J H,Wang Z W,Zhang H Y,et al.Occurrence and the fate of typical antibiotics in sewage treatment plants in Lanzhou[J].Acta Scientiae Circumstantiae,2016,36(10):3765-3773.