高级搜索

固相萃取-高效液相色谱-串联质谱法测定地表水中40种抗生素

,  ,  ,  ,  ,  ,  ,  , 

downloadPDF

上一篇

下一篇

王娅南, 彭洁, 谢双, 饶竹, 战楠, 黄心眉, 黄合田, 郭峰, 杨鸿波. 固相萃取-高效液相色谱-串联质谱法测定地表水中40种抗生素[J]. 环境化学, 2020, (1): 188-196. doi: 10.7524/j.issn.0254-6108.2019021304
引用本文: 王娅南, 彭洁, 谢双, 饶竹, 战楠, 黄心眉, 黄合田, 郭峰, 杨鸿波. 固相萃取-高效液相色谱-串联质谱法测定地表水中40种抗生素[J]. 环境化学, 2020, (1): 188-196. doi: 10.7524/j.issn.0254-6108.2019021304
shu
WANG Yanan, PENG Jie, XIE Shuang, RAO Zhu, ZHAN Nan, HUANG Xinmei, HUANG Hetian, GUO Feng, YANG Hongbo. Determination of 40 antibiotics in surface water by solid phase extraction-high performance liquid chromatography-tandem mass spectrometry[J]. Environmental Chemistry, 2020, (1): 188-196. doi: 10.7524/j.issn.0254-6108.2019021304
Citation: WANG Yanan, PENG Jie, XIE Shuang, RAO Zhu, ZHAN Nan, HUANG Xinmei, HUANG Hetian, GUO Feng, YANG Hongbo. Determination of 40 antibiotics in surface water by solid phase extraction-high performance liquid chromatography-tandem mass spectrometry[J]. Environmental Chemistry, 2020, (1): 188-196. doi: 10.7524/j.issn.0254-6108.2019021304
shu

固相萃取-高效液相色谱-串联质谱法测定地表水中40种抗生素

  • 1. 国家地质实验测试中心, 自然资源部生态地球化学重点实验室, 北京, 100037;

  • 2. 贵州省分析测试研究院, 贵阳, 550000;

  • 3. 贵阳市公共卫生救治中心, 贵阳, 550004;

  • 4. 贵州医科大学公共卫生学院, 贵阳, 550025

    • 通讯作者: 郭峰, E-mail: fengguo@cags.ac.cn ;  杨鸿波, E-mail: hbyang@gzata.cn
  • 基金项目:

    国家自然科学基金（21507017，21966011），国家国际科技合作专项（2015DFA41280）和中国地质调查局地质调查项目（DD20189627）资助.

Determination of 40 antibiotics in surface water by solid phase extraction-high performance liquid chromatography-tandem mass spectrometry

  • 1. National Research Center for Geoanalysis, Key Laboratory of Eco-Geochemistry, Ministry of Natural Resources, Beijing, 100037, China;

  • 2. Guizhou Academy of Testing and Analysis, Guiyang, 550000, China;

  • 3. Guiyang Public Health Clinical Center, Guiyang, 550004, China;

  • 4. Guizhou Medical University, School of Public Health, Guiyang, 550025, China

    • Corresponding authors: GUO Feng, fengguo@cags.ac.cn ;  YANG Hongbo, hbyang@gzata.cn
  • Fund Project: Supported by National Natural Science Foundation of China (21507017, 21966011), National International Science and Technology Cooperation Special Project (2015DFA41280) and China Geological Survey Project of China (DD20189627).

  • 摘要: 建立了固相萃取-高效液相色谱-串联质谱法（HLB-HPLC-MS/MS）分析地表水中15种磺胺类（SAs）、9种氟喹诺酮类（QNs）、7种大环内酯类（MCs）、3种四环素类（TCs）、2种氯霉素类（CAPs）和4种其他类（Others）共40种抗生素的分析方法.通过重点优化水样不同pH值、乙二胺四乙酸二钠（Na2EDTA）加入量、色谱条件和质谱参数等确定了最佳分析条件.水样经HLB固相萃取柱富集净化，采用Agilent Zorbax Rrhd Eclipse Plus C18（2.1 mm×50 mm，1.8 μm）色谱柱分离，正、负离子模式分别采集，正离子模式采用0.2%甲酸-2 mmol乙酸铵水溶液和甲醇-乙腈（V/V，1∶1）作流动相梯度洗脱分离38种单体；负离子模式采用纯水和甲醇-乙腈（V/V，1∶1）作流动相梯度分离2种单体，多重反应监测模式分析，内标法定量.结果显示：目标分析物线性范围在1.00—200 ng·mL-1之间，相关系数r2均大于0.99，方法检出限在0.002—0.270 ng·L-1之间，地表水加标回收率在61.0%—149%之间，相对标准偏差（RSD）在1.2%—32%之间.方法成功应用于贵阳市南明河12个地表水分析，共检出34种抗生素，其中大环内酯类检出浓度最高，平均浓度为257 ng·L-1.
    Abstract: A method was developed for the determination of 40 antibiotics including 15 sulfonamides (SAs), 9 fluoroquinolones (QNs), 7 macrolides (MCs), 3 tetracyclines (TCs), 2 chloramphenicols (CAPs) and 4 other classes in surface water by solid phase extraction coupled high performance liquid chromatography-tandem mass spectrometry (SPE-HPLC-MS/MS). The optimum analytical conditions were determined by optimizing the pH value of water samples, the amount of sodium ethylenediaminetetraacetate (Na2EDTA), chromatographic conditions and mass spectrometry parameters. HLB cartridge was selected to enrich and purify water samples. The analytes were separated on Agilent Zorbax Rrhd Eclipse Plus C18 columns (2.1 mm×50 mm, 1.8 μm) and were detected by positive and negative ion modes in multiple reaction monitoring (MRM) modes. In the positive mode, 38 antibiotics were separated by gradient elution with 0.2% formic acid and 2 mmol ammonium acetate in water and methanol-acetonitrile (V/V, 1:1) mixture. In negative mode, 2 antibiotics were separated by gradient elution with pure water and methanol-acetonitrile (V/V, 1:1) mixture. The antibiotics were quantified by internal standard method. The calibration range was from 1.00-200 ng·mL-1 with the correlation coefficients >0.99. The method limits of detection were in the range of 0.002-0.270 ng·L-1. The recoveries of target compounds at three spiked levels ranged from 61.0% to 149% with relative standard deviations of 1.23%-32.0%. The developed method was successfully applied to the analysis of 12 water samples from Nanming River in Guiyang City. In total 34 antibiotics were detected, of which macrolides were the predominant compounds with the average concentration of 257 ng·L-1.
  • 加载中
  • [1] KVMMERER K. Antibiotics in the aquatic environment:A review-part Ⅰ[J]. Chemosphere, 2009, 75(4):417-434.
    [2] KLEIN E Y, BOECKEL T P V, MARTINEZ E M, et al. Global increase and geographic convergence in antibiotic consumption between 2000 and 2015[J]. Proc Natl Acad Sci USA, 2018, 115(15):3463-3470.
    [3] LI W, SHI Y, GAO L, et al. Occurrence of antibiotics in water, sediments, aquatic plants, and animals from Baiyangdian Lake in North China[J]. Chemosphere, 2012, 89(11):1307-1315.
    [4] DENG W, LI N, ZHENG H, et al. Occurrence and risk assessment of antibiotics in river water in Hong Kong.[J]. Ecotoxicology & Environmental Safety, 2015, 125:121-127.
    [5] 胡譞予.水环境中抗生素对健康的危害[J].食品与药品, 2015,17(3):215-219.

    HU X Y. Harm of antibiotics in aquatic environment on health[J]. Food and Drug, 2015,17(3):215-219(in Chinese).

    [6] SKARIYACHAN S, MAHAJANAKATTI A B, GRANDHI N J, et al. Environmental monitoring of bacterial contamination and antibiotic resistance patterns of the fecal coliforms isolated from Cauvery River, a major drinking water source in Karnataka, India[J]. Environmental Monitoring and Assessment, 2015, 187(5):279-292.
    [7] VäLITALO P, KRUGLOVA A, MIKOLA A, et al. Toxicological impacts of antibiotics on aquatic micro-organisms:A mini-review[J]. International Journal of Hygiene & Environmental Health, 2017, 220(3):558-569.
    [8] 高立红, 史亚利, 厉文辉,等. 抗生素环境行为及其环境效应研究进展[J]. 环境化学, 2013, 32(9):1619-1633.

    GAO L H, SHI Y L, LI W H, et al. Advances in research on environmental behaviors and environmental effects of antibiotics[J]. Environmental Chemistry,2013, 32(9):1619-1633(in Chinese).

    [9] KIM C, RYU H D, CHUNG E G, et al. A review of analytical procedures for the simultaneous determination of medically important veterinary antibiotics in environmental water:Sample preparation, liquid chromatography, and mass spectrometry[J]. Journal of Environmental Management, 2018, 217:629-645.
    [10] DU J, ZHAO H, LIU S, et al. Antibiotics in the coastal water of the South Yellow Sea in China:Occurrence, distribution and ecological risks[J]. Science of the Total Environment, 2017, 595:521-527.
    [11] 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(12):123-138.
    [12] GROS M, RODRíGUEZMOZAZ 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(16):173-188.
    [13] SEIFRTOVÁ M, NOVÁKOVÁ L, LINO C, et al. An overview of analytical methodologies for the determination of antibiotics in environmental waters[J]. Analytica Chimica Acta, 2009, 649(2):158-179.
    [14] 高立红, 史亚利, 厉文辉,等. 高效液相色谱-电喷雾串联质谱法检测环境水样中22种抗生素类药物[J]. 色谱, 2010, 28(5):491-497

    GAO L H, SHI Y L, LI W H,et al. Determination of 22 antibiotics in environmental water samples using high performance liquid chromatography-electrosprayionization tandem masss pectrometry[J].Chineses Journal of Chromatography. 2010, 28(5):491-497(in Chinese).

    [15] PETROVI M, HERNANDO M D, DÍAZ-CRUZ M S, et al. Liquid chromatography-tandem mass spectrometry for the analysis of pharmaceutical residues in environmental samples:A review[J]. Journal of Chromatography A, 2005, 1067(1-2):1-14.
    [16] 罗方园, 潘根兴, 李恋卿,等. 洪泽湖沉积物中四环素土霉素及相关抗性基因的分布特征及潜在风险分析[J]. 农业环境科学学报, 2017, 36(2):369-375.

    LUO F Y, PAN G X, LI L Q, et al. The distribution characteristics and potential risk of tetracycline, oxytetracycline and their corresponding genes pollution in sediment of Hongze Lake[J]. Journal of Agro-Environment Science, 2017, 36(2):369-375(in Chinese).

    [17] MIAO X S, BISHAY F, CHEN M, et al. Occurrence of antimicrobials in the final effluents of wastewater treatment plants in Canada[J]. Environmental Science & Technology, 2004, 38(13):3533-3541.
    [18] GRUJIc' S, VASILJEVIc' T, LAUSEVIc' M. Determination of multiple pharmaceutical classes in surface and ground waters by liquid chromatography-ion trap-tandem mass spectrometry[J]. Journal of Chromatography A, 2009, 1216(25):4989-5000.
    [19] TAMTAM F, MERCIER F, EURIN J, et al. Ultra performance liquid chromatography tandem mass spectrometry performance evaluation for analysis of antibiotics in natural waters[J]. Analytical & Bioanalytical Chemistry, 2009, 393(6-7):1709-1718.
  • 加载中
WeChat 点击查看大图
计量
  • 文章访问数:  1179
  • HTML全文浏览数:  1179
  • PDF下载数:  88
  • 施引文献:  0
出版历程
  • 收稿日期:  2019-02-13
  • 刊出日期:  2020-01-01

固相萃取-高效液相色谱-串联质谱法测定地表水中40种抗生素

    通讯作者: 郭峰, E-mail: fengguo@cags.ac.cn ;  杨鸿波, E-mail: hbyang@gzata.cn
  • 1. 国家地质实验测试中心, 自然资源部生态地球化学重点实验室, 北京, 100037;
  • 2. 贵州省分析测试研究院, 贵阳, 550000;
  • 3. 贵阳市公共卫生救治中心, 贵阳, 550004;
  • 4. 贵州医科大学公共卫生学院, 贵阳, 550025
  • 收稿日期:  2019-02-13
  • 网络出版日期:  2020-01-01
基金项目:

国家自然科学基金（21507017，21966011），国家国际科技合作专项（2015DFA41280）和中国地质调查局地质调查项目（DD20189627）资助.

摘要: 建立了固相萃取-高效液相色谱-串联质谱法（HLB-HPLC-MS/MS）分析地表水中15种磺胺类（SAs）、9种氟喹诺酮类（QNs）、7种大环内酯类（MCs）、3种四环素类（TCs）、2种氯霉素类（CAPs）和4种其他类（Others）共40种抗生素的分析方法.通过重点优化水样不同pH值、乙二胺四乙酸二钠（Na2EDTA）加入量、色谱条件和质谱参数等确定了最佳分析条件.水样经HLB固相萃取柱富集净化，采用Agilent Zorbax Rrhd Eclipse Plus C18（2.1 mm×50 mm，1.8 μm）色谱柱分离，正、负离子模式分别采集，正离子模式采用0.2%甲酸-2 mmol乙酸铵水溶液和甲醇-乙腈（V/V，1∶1）作流动相梯度洗脱分离38种单体；负离子模式采用纯水和甲醇-乙腈（V/V，1∶1）作流动相梯度分离2种单体，多重反应监测模式分析，内标法定量.结果显示：目标分析物线性范围在1.00—200 ng·mL-1之间，相关系数r2均大于0.99，方法检出限在0.002—0.270 ng·L-1之间，地表水加标回收率在61.0%—149%之间，相对标准偏差（RSD）在1.2%—32%之间.方法成功应用于贵阳市南明河12个地表水分析，共检出34种抗生素，其中大环内酯类检出浓度最高，平均浓度为257 ng·L-1.

English Abstract

    全文HTML

参考文献 (19)

目录

/

返回文章
返回

Copyright © 2019 中国科学院生态环境研究中心