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QuEChERS-超高效液相色谱-串联质谱法检测花生中4种农药残留

杨松 邹楠 尤峥 于杰 王苓 宿莉 慕卫

杨松, 邹楠, 尤峥, 于杰, 王苓, 宿莉, 慕卫. QuEChERS-超高效液相色谱-串联质谱法检测花生中4种农药残留[J]. 农药学学报, 2021, 23(2): 414-420. doi: 10.16801/j.issn.1008-7303.2021.0023
引用本文: 杨松, 邹楠, 尤峥, 于杰, 王苓, 宿莉, 慕卫. QuEChERS-超高效液相色谱-串联质谱法检测花生中4种农药残留[J]. 农药学学报, 2021, 23(2): 414-420. doi: 10.16801/j.issn.1008-7303.2021.0023
Song YANG, Nan ZOU, Zheng YOU, Jie YU, Ling WANG, Li SU, Wei MU. Detection of 4 pesticides residues in peanut using QuEChERS-ultra high performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Pesticide Science, 2021, 23(2): 414-420. doi: 10.16801/j.issn.1008-7303.2021.0023
Citation: Song YANG, Nan ZOU, Zheng YOU, Jie YU, Ling WANG, Li SU, Wei MU. Detection of 4 pesticides residues in peanut using QuEChERS-ultra high performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Pesticide Science, 2021, 23(2): 414-420. doi: 10.16801/j.issn.1008-7303.2021.0023

QuEChERS-超高效液相色谱-串联质谱法检测花生中4种农药残留

doi: 10.16801/j.issn.1008-7303.2021.0023
基金项目: 广西创新驱动发展专项资金项目 (桂科AA17204043-1);山东省自然科学基金博士基金 (ZR2018BC038);科技部重点研发计划 (2016YFD0200206)
详细信息
    作者简介:

    杨松,男,硕士研究生,E-mail:yang_songhappy@163.com

    通讯作者:

    慕卫,通信作者 (Author for correspondence),女,教授,主要从事农药毒理学、农药残留分析及风险评估研究;E-mail:muwei@sdau.edu.cn

  • 中图分类号: TS207.5;O657.7;TQ450.263

Detection of 4 pesticides residues in peanut using QuEChERS-ultra high performance liquid chromatography-tandem mass spectrometry

  • 摘要: 建立了超高效液相色谱-串联质谱 (UPLC-MS/MS) 同时检测花生中精喹禾灵、毒死蜱、乙草胺和吡虫啉残留的分析方法。样品以纳米氧化锆 (Nano-ZrO2)、十八烷基键合硅胶 (C18) 和多壁碳纳米管 (MWCNT) 组合进行净化,采用UPLC-MS/MS检测,外标法定量。结果表明:在0.001~0.5 mg/L范围内,4种农药的质量浓度与其对应的峰面积间线性关系良好,r≥0.9986;在0.01、0.1和1 mg/kg 3个添加水平下,4种农药在花生中的平均回收率在82%~109%之间,相对标准偏差 (RSDs,n = 5) 在2.8%~9.0%之间,其定量限 (LOQ) 均为0.01 mg/kg。运用该方法对采自泰安市大型超市和农贸市场的10批次花生样品进行检测,结果表明,所有样品中4种农药的残留量均未超过中国规定的最大残留限量标准。该方法具有净化效果好、操作过程简便高效、灵敏度高、稳定性好和通用性强等优点,适用于花生中4种农药残留的同时检测。
  • 图  1  不同流动相体系下4种农药的响应强度 (n = 3)

    Figure  1.  Response intensity of 4 pesticides under different mobile phase systems (n = 3)

    图  2  当流动相为0.05%甲酸、2 mmoL/L乙酸铵水溶液时4种农药总离子流色谱图

    Figure  2.  Total ion current chromatograms of 4 pesticides when the mobile phase was 0.05% formic acid and 2 mmoL/L ammonium acetate aqueous solution

    图  3  PSA + Nano-ZrO2 (A)、PSA + C18 (B) 和Nano-ZrO2 + C18 (C) 净化剂组合下花生基质中4种农药的Me (n = 3)

    Figure  3.  Me of four pesticides in peanut matrix under the scavengers combination of PSA + Nano-ZrO2 (A), PSA + C18 (B) and Nano-ZrO2 + C18 (C) (n = 3)

    图  4  不同MWCNT用量下下花生基质中4种农药的 基质效应

    Figure  4.  Me of four pesticides in peanut matrix under different MWCNT dosages

    表  1  MRM模式下4种农药的质谱参数

    Table  1.   MS parameters of the 4 pesticides in MRM mode

    农药
    Pesticides
    保留时间
    Retention
    time/min
    监测离子对
    Monitoring ion
    pair, m/z
    锥孔电压
    Cone
    voltage/V
    碰撞能
    Collision
    energy/V
    精喹禾灵
    quizalofop-p-ethyl
    1.90 192.1/132.0* 33 18
    192.1/169.0 12
    吡虫啉
    imidacloprid
    0.84 256.1/175.1 34 20
    256.1/209.1* 15
    乙草胺
    acetochlor
    1.63 270.0/194.1* 21 17
    270.0/212.2 10
    毒死蜱
    chlorpyrifos
    2.09 349.9/132.0 28 22
    349.9/211.2* 12
    注 (Note):*定量离子对 (Quantitative ion)。
    下载: 导出CSV

    表  2  花生基质中3种净化剂组合及其用量

    Table  2.   The combination of three purifying agents in peanut matrix and their usage

    净化剂组合 
    Purifier combination 
    用量
    Dosage/mg
    PSA + Nano-ZrO2 10 + 40
    20 + 30
    25 + 25
    30 + 20
    40 + 10
    PSA + C18 10 + 40
    20 + 30
    25 + 25
    30 + 20
    40 + 10
    C18 + Nano-ZrO2 10 + 30
    20 + 20
    25 + 15
    30 + 10
    40 + 5
    下载: 导出CSV

    表  3  吡虫啉、乙草胺、精喹禾灵和毒死蜱在花生基质中的标准曲线、rMe和LOQ

    Table  3.   Standard curves, r, Me and LOQs of imidacloprid, acetochlor, quizalofop-p-ethyl and chlorpyrifos in peanut matrix

    农药  
    Pesticide  
    基质
    Matrix
    标准曲线
    Standard curve
    相关系数
    r
    基质效应
    Me
    精喹禾灵 quizalofop-p-ethyl 乙腈 Acetonitrile y = 2323441.5x − 10526.0 0.9992
    花生 Peanut y = 2202567.0x − 11573.5 0.9986 0.95
    吡虫啉 imidacloprid 乙腈 Acetonitrile y = 381939.5x + 322.8 0.9999
    花生 Peanut y = 354945.0x + 1640.2 0.9996 0.93
    乙草胺 acetochlor 乙腈 Acetonitrile y = 323519.2x − 1093.2 0.9997
    花生 Peanut y = 296498.0x − 158.7 0.9999 0.92
    毒死蜱 chlorpyrifos 乙腈 Acetonitrile y = 200834.0x − 317.1 0.9999
    花生 Peanut y = 191076.5x − 461.0 0.9992 0.95
    下载: 导出CSV

    表  4  花生基质中吡虫啉、乙草胺、精喹禾灵和毒死蜱的添加回收率和相对标准偏差 (n = 5)

    Table  4.   Recoveries and RSDs of imidacloprid, acetochlor, quizalofop-p-ethyl and chlorpyrifos in peanut matrix (n = 5)

    农药  
    Pesticide  
    添加水平 Spiked level/(mg/kg)
    0.01 0.1 1 (毒死蜱为 5)
    1(chlorpyrifos: 5)
    回收率 Recovery/%相对标准偏差 RSD/% 回收率 Recovery/%相对标准偏差 RSD/% 回收率 Recovery/%相对标准偏差 RSD/%
    精喹禾灵 quizalofop-p-ethyl 82 3.7 82 4.7 101 2.8
    吡虫啉 imidacloprid 109 5.8 102 3.6 90 8.7
    乙草胺 acetochlor 97 2.9 83 3.8 91 9.0
    毒死蜱 chlorpyrifos 94 8.0 106 3.2 96 2.8
    下载: 导出CSV

    表  5  花生实际样品的检测结果

    Table  5.   Monitoring results of peanut collected samples

    样品编号
    Samples No.
    残留量 Residue/(μg/kg)最大残留限量[18]
    MRLs/(mg/kg)
    超标情况
    Excessive situation
    精喹禾灵
    quizalofop-p-ethyl
    吡虫啉
    imidacloprid
    乙草胺
    acetochlor
    毒死蜱
    chlorpyrifos
    HS-Y1 0.3 0.5 (吡虫啉 imidacloprid) 不超标 No
    HS-Y2 0.56 2.45 0.5/0.2 (吡虫啉/毒死蜱 imidacloprid/chlorpyrifos) 不超标 No
    HS-Y3 2.69 0.2 不超标 No
    HS-Y4 0.47 0.5 2.78 0.5/0.1/0.2 (吡虫啉/乙草胺/毒死蜱imidacloprid/acetochlor/chlorpyrifos) 不超标 No
    HS-Y5 不超标 No
    HS-Y6 0.49 4.28 0.2 (毒死蜱 chlorpyrifos) 不超标 No
    HS-Y7 3.6 0.2 (毒死蜱 chlorpyrifos) 不超标 No
    HS-Y8 2.08 0.2 (毒死蜱 chlorpyrifos) 不超标 No
    HS-Y9 3.81 0.2 (毒死蜱 chlorpyrifos) 不超标 No
    HS-Y10 3.11 0.2 (毒死蜱 chlorpyrifos) 不超标 No
    下载: 导出CSV
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  • 收稿日期:  2020-05-09
  • 录用日期:  2020-08-08
  • 刊出日期:  2021-04-10

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