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非衍生化超高效液相色谱-串联质谱法快速检测环境水中强极性农药及其代谢物

方灵 史梦竹 司瑞茹 韦航 梁启富 傅建炜

方灵, 史梦竹, 司瑞茹, 韦航, 梁启富, 傅建炜. 非衍生化超高效液相色谱-串联质谱法快速检测环境水中强极性农药及其代谢物[J]. 农药学学报. doi: 10.16801/j.issn.1008-7303.2022.0128
引用本文: 方灵, 史梦竹, 司瑞茹, 韦航, 梁启富, 傅建炜. 非衍生化超高效液相色谱-串联质谱法快速检测环境水中强极性农药及其代谢物[J]. 农药学学报. doi: 10.16801/j.issn.1008-7303.2022.0128
FANG Ling, SHI Mengzhu, SI Ruiru, WEI Hang, LIANG Qifu, FU Jianwei. Nonderivatization method for determination of highly polar pesticides and their metabolites in environmental water by ultra-high performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Pesticide Science. doi: 10.16801/j.issn.1008-7303.2022.0128
Citation: FANG Ling, SHI Mengzhu, SI Ruiru, WEI Hang, LIANG Qifu, FU Jianwei. Nonderivatization method for determination of highly polar pesticides and their metabolites in environmental water by ultra-high performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Pesticide Science. doi: 10.16801/j.issn.1008-7303.2022.0128

非衍生化超高效液相色谱-串联质谱法快速检测环境水中强极性农药及其代谢物

doi: 10.16801/j.issn.1008-7303.2022.0128
基金项目: 福建省属公益项目 (2022R1022001);福建省农业科学院自由探索科技创新项目 (ZYTS202230);福建省农业科学院科技创新团队 (CXTD2021002);“5511”协同创新工程 (XTCXGC2021020).
详细信息
    作者简介:

    方灵,flonly@qq.com

    通讯作者:

    傅建炜,fjw9238@163.com

  • 中图分类号: X52;O657.63

Nonderivatization method for determination of highly polar pesticides and their metabolites in environmental water by ultra-high performance liquid chromatography-tandem mass spectrometry

Funds: Fujian Public Welfare Project (2022R1022001);Free Exploration of Science and Technology Innovation Project of Fujian Academy of Agricultural Sciences (ZYTS202230);Science and Technology Innovation Team Project of Fujian Academy of Agricultural Sciences (CXTD2021002);"5511" Collaborative Innovation Project (XTCXGC2021020).
  • 摘要: 建立了一种简便、直接进样、非衍生化超高效液相色谱-串联质谱 (UPLC-MS/MS) 快速测定环境水样中乙烯利、草甘膦、草铵膦及其代谢物等6种强极性化合物残留的分析检测方法。环境水样经离心、过滤后,无需衍生,直接进样进行定量分析。样品经Waters Acquity UPLC HSS T3色谱柱 (100 mm × 2.1 mm,1.8 µm) 分离,以0.1%甲酸-5 μmol/L亚甲基二膦酸水溶液、甲醇为流动相,在电喷雾离子源、正负离子扫描和多反应监测模式 (MRM) 下进行分析,外标法定量。结果表明:6种化合物在各自线性范围内具有良好的线性关系,决定系数 (R2) 均大于0.99,在10~200 µg/L添加水平下,6种化合物在环境水样中的平均回收率在75%~100%之间,日内相对标准偏差与日间相对标准偏差(n=6)分别为3.6%~7.0%和4.3%~7.5%。方法定量限在0.5~10.0 µg/L之间。利用所建立的方法对3个地区10份地表水样进行检测。结果显示:乙烯利、草甘膦、草铵膦及其代谢物等6种化合物均未检出。该方法与衍生化方法相比,具有简便快速、重现性好、灵敏度高等优点,可以为环境水中乙烯利、草甘膦、草铵膦及其代谢物等强极性化合物检测提供参考。
  • 1  6种化合物化学结构

    1.  Chemical structures of six compounds

    图  1  采用不同流动相水相时6种化合物响应强度 (n=3)

    Figure  1.  Response of six compounds using different water phase of mobile phase (n=3)

    图  2  不同浓度亚甲基二膦酸对6种化合物信号响应强度的影响 (n=3)

    Figure  2.  Effect of different concentrations of medronic acid (0, 2.5, 5, 10, 15 µmol/L) on peak area of six compounds (n=3)

    图  3  6种化合物的提取离子流色谱图(500 µg/L)

    Figure  3.  Extracted ion chromatogram of six compounds(500 µg/L)

    图  4  进样系统中3-甲基磷酸亚基丙酸残留水平试验 (n=3)

    Figure  4.  Residual level of MPPA in injection system (n=3)

    表  1  6种化合物的质谱信息参数

    Table  1.   The MS parameters of the six compounds

    编号
    No.
    化合物    
    Compound    
    保留时间
    Retention
    time/min
    前体离子
    Precursor
    Ion, m/z
    产物离子
    Product
    ion, m/z
    Q1预杆电压
    Q1 Pre
    Bias/V
    Q3预杆电压
    Q3 Pre
    Bias/V
    碰撞能量
    Collision
    energy/eV
    模式
    Mode
    1 草甘膦 Gly 1.338 170.05 42.15/88.05* −14/−15 −17/−17 −30/−12 ESI+
    2 草铵膦 Glu 1.355 182.30. 56.05/136.20* −15/−12 −20/−26 −31/−13 ESI+
    3 氨甲基膦酸 AMPA 1.306 112.15 29.95*/47.05 −15/−11 −30/−19 −20/−48 ESI+
    4 3-甲基磷酸亚基丙酸 MPPA 1.530 153.15 62.90/135.05* 17/29 21/12 24/16 ESI-
    5 草铵膦-N−乙酰 NAG 2.194 224.00 56.0/136.0* −18/−15 −15/−20 −30/−20 ESI+
    6 乙烯利 ETH 2.055 145.10 81.00*/91.05 −14/−12 −17/−18 −22/−18 ESI+
    注:*为定量离子 (quantitative ion).
    下载: 导出CSV

    表  2  6种化合物在空白水样中的添加回收率、相对标准偏差、LOD及LOQ (n=6)

    Table  2.   Recoveries, RSD, LOD, and LOQ for six compounds in blank water samples (n=6)

    化合物
    Compound
    添加水平 Spiked level检出限
    LOD/
    (µg/L)
    定量限
    LOQ/
    (µg/L)
    10 µg/L50 µg/L200 µg/L
    回收率
    Recovery/
    %
    日内
    RSD
    Intra-day
    RSD/%
    日间
    RSD
    Inter-day
    RSD/%
    回收率
    Recovery/
    %
    日内
    RSD
    Intra-day
    RSD/%
    日间
    RSD
    Inter-day
    RSD/%
    回收率
    Recovery/
    %
    日内
    RSD
    Intra-day
    RSD/%
    日间
    RSD
    Inter-day
    RSD/%
    Gly866.97.0866.76.9965.66.61.03.0
    Glu787.07.5975.86.2985.16.70.251.0
    AMPA845.36.1894.35.6884.85.93.010.0
    MPPA865.46.8984.24.8894.14.32.06.0
    NAG904.54.8963.85.7963.64.60.10.5
    ETH756.87.21005.56.5876.66.92.06.0
    注:Gly:草甘膦;Glu:草铵膦;AMPA:氨甲基磷酸;MPPA:3-甲基磷酸亚基丙酸;NAG:草铵膦-N-乙酰;ETH:乙烯利。
    下载: 导出CSV
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  • 收稿日期:  2022-08-01
  • 录用日期:  2022-11-01
  • 网络出版日期:  2022-11-09

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