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滤过型净化柱净化-超高效液相色谱-三重四极杆/复合线性离子阱质谱法测定草鱼中11种农药残留

封腾望 王新新 周锐东 刘欢 孙慧武 李晋成

封腾望, 王新新, 周锐东, 刘欢, 孙慧武, 李晋成. 滤过型净化柱净化-超高效液相色谱-三重四极杆/复合线性离子阱质谱法测定草鱼中11种农药残留[J]. 农药学学报, 2022, 24(5): 1268-1277. doi: 10.16801/j.issn.1008-7303.2022.0097
引用本文: 封腾望, 王新新, 周锐东, 刘欢, 孙慧武, 李晋成. 滤过型净化柱净化-超高效液相色谱-三重四极杆/复合线性离子阱质谱法测定草鱼中11种农药残留[J]. 农药学学报, 2022, 24(5): 1268-1277. doi: 10.16801/j.issn.1008-7303.2022.0097
FENG Tengwang, WANG Xinxin, ZHOU Ruidong, LIU Huan, SUN Huiwu, LI Jincheng. Determination of 11 pesticides residues in grass carp using ultra-performance liquid chromatography/quadrupole-linear ion trap mass spectrometry coupled with pass-through clean-up column[J]. Chinese Journal of Pesticide Science, 2022, 24(5): 1268-1277. doi: 10.16801/j.issn.1008-7303.2022.0097
Citation: FENG Tengwang, WANG Xinxin, ZHOU Ruidong, LIU Huan, SUN Huiwu, LI Jincheng. Determination of 11 pesticides residues in grass carp using ultra-performance liquid chromatography/quadrupole-linear ion trap mass spectrometry coupled with pass-through clean-up column[J]. Chinese Journal of Pesticide Science, 2022, 24(5): 1268-1277. doi: 10.16801/j.issn.1008-7303.2022.0097

滤过型净化柱净化-超高效液相色谱-三重四极杆/复合线性离子阱质谱法测定草鱼中11种农药残留

doi: 10.16801/j.issn.1008-7303.2022.0097
基金项目: 中央级公益性科研院所基本科研业务费 (2020B005);中国水产科学研究院科技创新项目 (2020TD75)
详细信息
    作者简介:

    封腾望,2845542303@qq.com

    通讯作者:

    李晋成,lijc@cafs.ac.cn

  • 中图分类号: TQ450.2;O657.63

Determination of 11 pesticides residues in grass carp using ultra-performance liquid chromatography/quadrupole-linear ion trap mass spectrometry coupled with pass-through clean-up column

Funds: Basic Scientific Research Expenses of Central Public Welfare Scientific Research Institutes (2020B005); Scientific and Technological Innovation Project of Chinese Academy of Fisheries Sciences (2020TD75).
  • 摘要: 采用推杆式滤过型净化柱净化,结合超高效液相色谱-三重四极杆/复合线性离子阱质谱仪(UPLC-QTRAP-MS/MS)建立了草鱼样品中11种农药残留的检测方法。以乙腈为提取剂,样品经超声、冷冻、离心后,上清液采用以50 mg PSA为净化填料的推杆式滤过型净化柱进行1次快速净化;超高效液相色谱快速分离,三重四极杆/复合线性离子阱质谱仪进行测定。基质匹配法制作标准曲线,外标法定量。结果表明:11种农药在1.0~50.0 μg/kg内的线性关系良好,相关系数均大于0.99;定量限为1.0~2.0 µg/kg。不同添加水平下的回收率为83%~119%,日内相对标准偏差为2.6%~20%,日间相对标准偏差为0.7%~15%。该方法经济、简便、高效,灵敏度高,重复性好,可作为草鱼中农药残留的日常检测方法。
  • 1  11种农药的化学结构式

    1.  Chemical structural formulas of 11 pesticides

    图  1  CAFS clean-up column净化流程[27]

    Figure  1.  The procedure of CAFS clean-up column[27]

    图  2  草鱼样品中11种农药的色谱图 (1LOQ)

    Figure  2.  Chromatograms of 11 pesticides in grass carp sample spiked an LOQ level

    图  3  乙腈和V (甲酸) : V(乙腈) = 1 : 999对草鱼样品中11种农药的提取效果对比 (n = 3)

    Figure  3.  Comparison of extraction effects of 11 pesticides in grass carp using acetonitrile and acetonitrile containing 0.1% formic acid (n = 3)

    图  4  不同净化填料对草鱼样品中11种农药回收率的影响 (n=3)

    Figure  4.  Effects of different types of purification sorbents on recoveries of 11 pesticides in grass carp (n=3)

    图  5  不同质量净化填料对草鱼样品中11种农药回收率的影响 (n=3)

    Figure  5.  Effect of different amount of purification sorbents on recoveries of 11 pesticides in grass carp (n=3)

    图  6  不同净化次数对草鱼样品中11种农药回收率的影响 (n=3)

    Figure  6.  Effect of different cleanup times on recoveries of 11 pesticides in grass carp (n=3)

    图  7  11种农药的基质效应

    Figure  7.  Matrix effects of 11 pesticides

    表  1  梯度洗脱程序

    Table  1.   The gradient elution program

    时间
    Time/min
    流速
    Flow rate/(mL/min)
    流动相A
    Mobile phase A/%
    流动相B
    Mobile phase B/%
    00.360.040.0
    1.000.360.040.0
    12.000.35.095.0
    14.000.35.095.0
    15.500.360.040.0
    20.000.360.040.0
    下载: 导出CSV

    表  2  11种农药的质谱参数

    Table  2.   Mass spectrum parameters of 11 pesticides

    农药  
    Pesticide  
    前体离子
    Precursor ion,m/z
    产物离子
    Product ion,m/z
    驻留时间
    Dwell time/ms
    碰撞能量
    Collision energy/V
    杀线威 thioxamyl 237.1 72.0*, 90.1 100.0 32,11
    残杀威 propoxur 210.1 111.0*, 168.1 100.0 18,11
    异丙威 isoprocarb 194.1 95.0*, 137.2 100.0 22,12
    甲硫威 methiocarb 226.0 169.1*, 121.0 100.0 15,24
    仲丁威 fenobucarb 208.1 95.1*, 152.1 100.0 20,11
    克百威 carbofuran 222.1 165.1*, 123.1 100.0 16,32
    甲萘威 carbaryl 202.1 145.1*, 117.0 100.0 16,34
    速灭威 metolcarb 166.1 109.0*, 94.1 100.0 20,37
    乐果 dimethoate 230.0 125.0*, 199.0 100.0 29,13
    灭线磷 ethoprophos 243.1 173.0*, 130.9 100.0 19,28
    扑草净 prometryn 242.1 158.1*, 200.1 100.0 32,25
    注:*定量离子。Note: *Quantitative ion.
    下载: 导出CSV

    表  3  11种农药的标准曲线和定量限

    Table  3.   Standard curves and limit of quantifications of 11 pesticides

    农药  
    Pesticide  
    线性范围
    Linear range/(µg/kg)
    回归方程
    Regression equation
    相关系数
    r
    定量限
    LOQ/(µg/kg)
    杀线威 thioxamyl 1.0~50.0 y = 6548.3x + 4945.8 0.99162 1.0
    残杀威 propoxur 1.0~50.0 y = 16902.0x + 1064.6 0.99725 1.0
    异丙威 isoprocarb 1.0~50.0 y = 20955.4x + 1464.5 0.99837 1.0
    甲硫威 methiocarb 1.0~50.0 y = 13319.8x + 1745.7 0.99925 1.0
    仲丁威 fenobucarb 1.0~50.0 y = 24871.6x-1225.3 0.99954 1.0
    克百威 carbofuran 1.0~50.0 y = 49637.2x + 2304.3 0.99839 1.0
    甲萘威 carbaryl 2.0~50.0 y = 15872.8x + 7184.0 0.99815 2.0
    速灭威 metolcarb 1.0~50.0 y = 13280.6x + 547.9 0.99829 1.0
    乐果 dimethoate 1.0~50.0 y = 16521.2x + 325.6 0.99921 1.0
    灭线磷 ethoprophos 1.0~50.0 y = 34662.9x + 878.4 0.99973 1.0
    扑草净 prometryn 1.0~50.0 y = 32431.6x-9783.7 0.99976 1.0
    下载: 导出CSV

    表  4  草鱼中11种农药的回收率和相对标准偏差 (n=6)

    Table  4.   Recoveries and RSD of 11 pesticides in grass carp (n=6)

    农药
    Pesticide
    添加水平
    Spiked level/
    (μg/kg)
    平均回收率
    Average
    recovery/%
    日内相对
    标准偏差
    Intra day
    RSD/%
    日间相对
    标准偏差
    Inter day
    RSD/%
    杀线威 thioxamyl 1.0 119 10 14
    2.0 102 11 5.2
    10.0 104 7.6 9.3
    残杀威 propoxur 1.0 98 6.6 5.6
    2.0 98 6.6 5.1
    10.0 99 4.4 6.4
    异丙威 isoprocarb 1.0 91 13 9.5
    2.0 102 14 5.8
    10.0 96 4.8 11
    甲硫威 methiocarb 1.0 102 12 15
    2.0 103 11 13
    10.0 99 5.3 3.2
    仲丁威 fenobucarb 1.0 110 4.5 6.1
    2.0 108 8.8 2.6
    10.0 96 4.2 8.6
    克百威 carbofuran 1.0 100 5.0 11
    2.0 103 5.9 5.3
    10.0 101 4.2 3.1
    甲萘威 carbaryl 2.0 113 15 5.6
    4.0 104 8.1 9.7
    20.0 93 4.1 8.6
    速灭威 metolcarb 1.0 110 9.4 9.2
    2.0 98 10 5.0
    10.0 97 5.2 0.8
    乐果 dimethoate 1.0 103 20 2.4
    2.0 103 3.8 0.7
    10.0 98 2.6 0.9
    灭线磷 ethoprophos 1.0 83 13 15
    2.0 99 5.9 13
    10.0 101 9.0 15
    扑草净 prometryn 1.0 93 9.0 6.3
    2.0 102 16 13
    10.0 88 9.9 6.1
    下载: 导出CSV
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  • 收稿日期:  2022-06-27
  • 录用日期:  2022-08-29
  • 网络出版日期:  2022-09-15
  • 刊出日期:  2022-10-10

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