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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

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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.
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  • 收稿日期:  2019-02-13
  • 刊出日期:  2020-01-01
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

    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.

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