高级搜索

超高效液相色谱-串联质谱法同时测定环境水样中的15种抗生素

,  ,  ,  ,  ,  , 

downloadPDF

上一篇

下一篇

崔敬鑫, 石秋俊, 王国民, 唐柏彬, 邱德生, 魏世强, 张进忠. 超高效液相色谱-串联质谱法同时测定环境水样中的15种抗生素[J]. 环境化学, 2020, (4): 1065-1074. doi: 10.7524/j.issn.0254-6108.2019042902
引用本文: 崔敬鑫, 石秋俊, 王国民, 唐柏彬, 邱德生, 魏世强, 张进忠. 超高效液相色谱-串联质谱法同时测定环境水样中的15种抗生素[J]. 环境化学, 2020, (4): 1065-1074. doi: 10.7524/j.issn.0254-6108.2019042902
shu
CUI Jingxin, SHI Qiujun, WANG Guomin, TANG Bobin, QIU Desheng, WEI Shiqiang, ZHANG Jinzhong. Simultaneous determination of 15 antibiotics in environmental water samples by ultra performance liquid chromatography- tandem mass spectrometry[J]. Environmental Chemistry, 2020, (4): 1065-1074. doi: 10.7524/j.issn.0254-6108.2019042902
Citation: CUI Jingxin, SHI Qiujun, WANG Guomin, TANG Bobin, QIU Desheng, WEI Shiqiang, ZHANG Jinzhong. Simultaneous determination of 15 antibiotics in environmental water samples by ultra performance liquid chromatography- tandem mass spectrometry[J]. Environmental Chemistry, 2020, (4): 1065-1074. doi: 10.7524/j.issn.0254-6108.2019042902
shu

超高效液相色谱-串联质谱法同时测定环境水样中的15种抗生素

  • 1. 西南大学资源环境学院, 重庆市农业资源与环境重点实验室, 重庆, 400715;

  • 2. 重庆海关技术中心, 重庆, 400020;

  • 3. 营山县环境监测站, 南充, 637700

    • 通讯作者: 张进忠, E-mail: jzhzhang@swu.edu.cn
  • 基金项目:

    重庆市技术创新与应用示范专项重点研发项目（cstc2018jszx-zdyfxmX0002）和国家重点研发计划项目（2018YFD0800601）资助.

Simultaneous determination of 15 antibiotics in environmental water samples by ultra performance liquid chromatography- tandem mass spectrometry

  • 1. College of Resources and Environment, Southwest University, Chongqing Key Laboratory of Agricultural Resources and Environment, Chongqing, 400715, China;

  • 2. Technical Center, Chongqing Customs, Chongqing, 400020, China;

  • 3. Environmental Monitoring Station of Yingshan County, Nanchong, 637700, China

    • Corresponding author: ZHANG Jinzhong, jzhzhang@swu.edu.cn
  • Fund Project: Supported by Chongqing Key Research & Development Program of Technology Innovation and Application Demonstration (cstc2018jszx-zdyfxmX0002) and the National Key Research & Development Program of China (2018YFD0800601).

  • 摘要: 采用固相萃取/超高效液相色谱-串联质谱法，建立了水样中磺胺类、四环素类、氟喹诺酮类、大环内酯类和氯霉素类15种抗生素的同时测定方法.水样经HLB固相萃取柱富集，ACQUITY UPLC BEH C18色谱柱分离，以乙腈和5 mmol·L-1乙酸铵溶液（含0.1%甲酸）为流动相梯度洗脱，电喷雾离子源-串联质谱多反应监测模式检测.结果表明，同时测定15种抗生素的线性范围为5-100 μg·L-1（相关系数均大于0.997），检出限为2.1-22.0 ng·L-1，定量限为6.9-71.8 ng·L-1；空白水样在加标水平为5、10、20 μg·L-1时，抗生素的回收率为50.1%-109.0%，相对标准偏差为0.4%-8.5%（n=7）.用本文建立的方法检测某农业小流域环境水样，发现5类抗生素可被不同程度检出，浓度范围为0.1-106.2 ng·L-1.
    Abstract: A simultaneous determination method for 15 antibiotics including sulfonamides, tetracyclines, quinolones, macrolides and chloramphenicols in water samples was developed by ultra performance liquid chromatography-tandem mass spectrometry with solid-phase extraction. The antibiotics in water samples were enriched by HLB solid-phase extraction column, and separated by ACQUITY UPLC BEH C18 column and eluted by acetonitrile and 5 mmol·L-1 ammonium acetate solution containing 0.1% formic acid as the mobile phases with gradient elution, and then determined by electrospray ion source-tandem mass spectrometry with multi-reaction monitoring mode. The results showed that the linear ranges were 5—100 μg·L-1 (R ≥ 0.997) with the detection limits of 2.1—22.0 ng·L-1 and the limits of quantification of 6.9—71.8 ng·L-1 for the simultaneous determination of 15 antibiotics. The recoveries of blank water sample spiked with 5, 10 and 20 μg·L-1 antibiotic standards were in the range of 50.1%—109.0% (0.4%≤RSDs≤8.5%, n=7). The five kinds of antibiotics in environmental water samples of an agricultural watershed could be detected with the range of 0.1—106.2 ng·L-1 by using the developed method in this study.
  • 加载中
  • [1] 张国栋,董文平,刘晓晖,等.我国水环境中抗生素赋存、归趋及风险评估研究进展[J]. 环境化学,2018,37(7):1491-1500.

    ZHANG G D, DONG W P, LIU X H, et al. Occurrence, fate and risk assessment of antibiotics in water environment of China[J]. Environmental Chemistry, 2018, 37(7):1491-1500(in Chinese).

    [2] AUST M O, GODLINSKI F, TRAVIS G R, et al. Distribution of sulfamethazine, chlortetracycline and tylosin in manure and soil of Canadian feedlots after subtherapeutic use in cattle[J]. Environmental Pollution, 2008, 156:1243-1251.
    [3] 周爱霞,苏小四,高松,等.高效液相色谱测定地下水、土壤及粪便中4种磺胺类抗生素[J]. 分析化学,2014,42(3):397-402.

    ZHOU A X, SU X S, GAO S, et al. Determination of four sulfa antibiotics in groundwater, soil and excreta samples using high performance liquid chromatography[J]. Chinese Journal of Analytical Chemistry, 2014, 42(3):397-402(in Chinese).

    [4] 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]. Environment Pollution, 2013, 175:22-29.
    [5] LI W H, SHI Y L, GAO L H, et al. Occurrence and removal of antibiotics in a municipal wastewater reclamation plant in Beijing, China[J]. Chemosphere, 2013, 92(4):435-444.
    [6] 刘昔,王智,王学雷,等.我国典型区域地表水环境中抗生素污染现状及其生态风险评价[J]. 环境科学,2019,40(5):2094-2100.

    LIU X, WANG Z, WANG X L, et al. Status of antibiotic contamination and ecological risks assessment in Chinese several typical surface-water environment[J]. Environmental Science, 2019, 40(5):2094-2100(in Chinese).

    [7] 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.
    [8] 章强,辛琦,朱静敏,等.中国主要水域抗生素污染现状及其生态环境效应研究进展[J]. 环境化学,2014,33(7):1075-1083.

    ZHANG Q, XIN Q, ZHU J M, et al. The antibiotic contaminations in the main water bodies in China and the associated environmental and human health impacts[J]. Environmental Chemistry, 2014, 33(7):1075-1083(in Chinese).

    [9] ZHANG Q Q, YING G G, PAN C G, et al. A comprehensive evaluation of antibiotics emission and fate in the river basins of China:Source analysis, multimedia modeling, and linkage to bacterial resistence[J]. Environmental Science & Technology, 2015, 49(11):6772-6782.
    [10] 宋淑敏,张翔宇,周佳虹,等.超高效液相色谱串联质谱法同时测定城市污水处理厂污泥中12种抗生素[J]. 环境化学,2017,36(9):1923-1931.

    SONG S M, ZHANG X Y, ZHOU J H, et al. Simultaneous determination of 12 antibiotics in sewage sludge by ultra performance liquid chromatography-electrospray ionization tandem mass spectrometry[J]. Environmental Chemistry, 2017, 36(9):1923-1931(in Chinese).

    [11] 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(in Chinese).

    [12] 程家兴,赵起越,李令军,等.固相萃取/超高效液相色谱-质谱法筛查及检测养鱼河水中抗生素[J]. 分析测试学报,2018,37(3):275-281.

    CHENG J X, ZHAO Q Y, LI L J, et al. Screening and detection of antibiotics in fish pond water by ultra performance liquid chromatography-mass spectrometry with solid phase extraction[J]. Journal of Instrumental Analysis, 2018, 37(3):275-281(in Chinese).

    [13] 张金,宗栋良,常爱敏,等.水环境中典型抗生素SPE-UPLC-MS/MS检测方法的建立[J]. 环境化学,2015,34(8):1446-1452.

    ZHANG J, ZONG D L, CHANG A M, et al. Determination of common antibiotics in aquatic environment by solid-phase extraction and ultra pressure liquid chromatography-tandem mass spectrometry (UPLC-MS/MS)[J]. Environmental Chemistry, 2015, 34(8):1446-1452(in Chinese).

    [14] 李经纬,丁紫荣,余乐洹,等.高效液相色谱-串联质谱法同时检测水中17种抗生素[J]. 分析科学学报,2016,32(6):51-856.

    LI J W, DING Z R, YU L H, et al. Determination of seventeen antibiotics in water by liquid chromatography-tandem mass spectrometry[J]. Journal of Analytical Science, 2016, 32(6):851-856(in Chinese).

    [15] KUMAR K, THOMPSON A, SINGH A K, et al. Enzyme-linked immunosorbent assay for ultratrace determination of antibiotics in aqueous samples[J]. Journal of Environmental Quality, 2004, 33(1):250-256.
    [16] HE T, XU Z Q, REN J. Pressure-assisted electrokinetic injection stacking for seven typical antibiotics in waters to achieve μg/L level analysis by capillary electrophoresis with UV detection[J]. Microchemical Journal, 2019, 146:1295-1300.
    [17] TURIEL E, BORDIN G, RODNGUEZ A R. Trace enrichment of (fluoro) quinolone antibiotics in surface waters by solid-phase extraction and their determination by liquid chromatography-ultraviolet detection[J]. Journal of Chromatography A, 2003, 1008:145-155.
    [18] 谭建华,唐才明,余以义,等.高效液相色谱法同时分析城市河水中的多种抗生素[J]. 色谱,2007,25(4):546-549.

    TAN J H, TANG C M, YU Y Y, et al. Simultaneous analysis of multiple classes of antibiotics in urban river water by high performance liquid chromatography[J]. Chinese Journal of Chromatography, 2007, 25(4):546-549(in Chinese).

    [19] 赵立军,郭磊,陈进富,等.抗生素废水的GC-MS分析与显色物质的初步确定[J]. 环境工程学报,2009,3(10):1830-1834.

    ZHAO L J, GUO L, CHEN J F, et al. GC-MS analysis of antibiotic waste water and preliminary determination of color material[J]. Chinese Journal of Environmental Engineering, 2009, 3(10):1830-1834(in Chinese).

    [20] TAHERGORABI M, ESRAFILIA A, KWEMANI M, et al. Degradation of four antibiotics from aqueous solution by ozonation:Intermediates identification and reaction pathways[J]. Desalination and Water Treatment, 2019, 139:277-287.
    [21] LINDSEY M, MEYER M, THURMAN E M. Analysis of trace levels of sulfonamide and tetracycline antimicrobials in groundwater and surface water using solid-phase extraction and liquid chromatography/mass spectrometry[J]. Analytical Chemistry, 2001, 73:4640-4646.
    [22] CAHILL J D, FURLONG E T, BURKHARDT M R, et al. Determination of pharmaceutical compounds in surface-and ground-water samples by solid-phase extraction and high-performance liquid chromatography-electrospray ionization mass spectrometry[J]. Journal of Chromatography A, 2004, 1041:171-180.
    [23] 黄秋鑫,陈琼,雷敏,等.同位素内标稀释高效液相色谱-质谱法同时测定水中多种痕量抗生素[J]. 环境化学,2016,35(7):1493-1499.

    HUANG Q X, CHEN Q, LEI M, et al. Simultaneous determination of trace antibiotics in surface water by isotope-diluted high performance liquid chromatography-mass spectrometry[J]. Environmental Chemistry, 2016, 35(7):1493-1499(in Chinese).

    [24] ZHOU L J, YING G G, LIU S, et al. Simultaneous determination of human and veterinary antibiotics in various environmental matrices by rapid resolution liquid chromatography-electrospray ionization tandem mass spectrometry[J]. Journal of Chromatography A, 2012, 1244:123-138.
    [25] PANDITI V R, BATCHU S R, GA R, et al. Online solid-phase extraction-liquid chromatography-electrospray-tandem mass spectrometry determination of multiple classes of antibiotics in environmental and treated waters[J]. Analytical and Bioanalytical Chemistry, 2013, 405(18):5953-5964.
    [26] 杜鹃,赵洪霞,陈景文.固相萃取-高效液相色谱-串联质谱法同时测定养殖海水中23种抗生素[J]. 色谱,2015,33(4):348-353.

    DU J, ZHAO H X, CHEN J W. Simultaneous determination of 23 antibiotics in mariculture water using solid-phase extraction and high performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2015, 33(4):348-353(in Chinese).

    [27] MOKH S, KHATIB E M, KOUBAR M, et al. Innovative SPE-LC-MS/MS technique for the assessment of 63 pharmaceuticals and the detection of antibiotic-resistant-bacteria:A case study natural water sources in Lebanon[J]. Science of the Total Environment, 2017, 609:830-841.
    [28] MIOSSEC C, LANCELEUE L, MONPERRUS M. Multi-residue analysis of 44 pharmaceutical compounds in environmental water samples by solid-phase extraction coupled to liquid chromatography-tandem mass spectrometry[J]. Journal of Separation Science, 2019,DOI:10.1002/jssc.201801214.
    [29] 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(in Chinese).

    [30] NEGREANU Y, PASTERNAKk Z, JURKEVITCH E, et al. Impact of treated wastewater irrigation on antibiotic resistance in agricultural soils[J]. Environmental Science & Technology, 2012, 46(9):4800-4808.
    [31] 董恒涛,姚劲挺,郝红元,等.超高效液相色谱三重四极杆质谱联用法测定地表水中14种喹诺酮类抗生素残留[J]. 环境化学,2018,37(6):1436-1439.

    DONG H T, YAO J T, HAO H Y, et al. Determination of 14 quinolones residues in surface water by UHPLC-MS/MS[J]. Environmental Chemistry, 2018, 37(6):1436-1439(in Chinese).

    [32] GROS M, RODRÍGUEZ-MOZAZ S, BARCELÓ D. Rapid analysis of multiclass antibiotic residues and some of their metabolites in hospital, urban wastewater and river water by ultra-high-performance liquid chromatography coupled to quadrupole-linear ion trap tandem mass spectrometry[J]. Journal of Chromatography A, 2013, 1292:173-188.
  • 加载中
WeChat 点击查看大图
计量
  • 文章访问数:  2054
  • HTML全文浏览数:  2054
  • PDF下载数:  70
  • 施引文献:  0
出版历程
  • 收稿日期:  2019-04-29

超高效液相色谱-串联质谱法同时测定环境水样中的15种抗生素

    通讯作者: 张进忠, E-mail: jzhzhang@swu.edu.cn
  • 1. 西南大学资源环境学院, 重庆市农业资源与环境重点实验室, 重庆, 400715;
  • 2. 重庆海关技术中心, 重庆, 400020;
  • 3. 营山县环境监测站, 南充, 637700
  • 收稿日期:  2019-04-29
基金项目:

重庆市技术创新与应用示范专项重点研发项目（cstc2018jszx-zdyfxmX0002）和国家重点研发计划项目（2018YFD0800601）资助.

摘要: 采用固相萃取/超高效液相色谱-串联质谱法，建立了水样中磺胺类、四环素类、氟喹诺酮类、大环内酯类和氯霉素类15种抗生素的同时测定方法.水样经HLB固相萃取柱富集，ACQUITY UPLC BEH C18色谱柱分离，以乙腈和5 mmol·L-1乙酸铵溶液（含0.1%甲酸）为流动相梯度洗脱，电喷雾离子源-串联质谱多反应监测模式检测.结果表明，同时测定15种抗生素的线性范围为5-100 μg·L-1（相关系数均大于0.997），检出限为2.1-22.0 ng·L-1，定量限为6.9-71.8 ng·L-1；空白水样在加标水平为5、10、20 μg·L-1时，抗生素的回收率为50.1%-109.0%，相对标准偏差为0.4%-8.5%（n=7）.用本文建立的方法检测某农业小流域环境水样，发现5类抗生素可被不同程度检出，浓度范围为0.1-106.2 ng·L-1.

English Abstract

    全文HTML

参考文献 (32)

目录

/

返回文章
返回

Copyright © 2019 中国科学院生态环境研究中心