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QuEChERS-高效液相色谱-串联质谱法检测 氟吡菌胺及其代谢物和霜霉威在叶用 莴苣中的残留及消解动态

唐红霞 黄佳庆 孙强 温广月 董茂锋 王伟民

唐红霞, 黄佳庆, 孙强, 温广月, 董茂锋, 王伟民. QuEChERS-高效液相色谱-串联质谱法检测 氟吡菌胺及其代谢物和霜霉威在叶用 莴苣中的残留及消解动态[J]. 农药学学报, 2021, 23(2): 388-394. doi: 10.16801/j.issn.1008-7303.2021.0026
引用本文: 唐红霞, 黄佳庆, 孙强, 温广月, 董茂锋, 王伟民. QuEChERS-高效液相色谱-串联质谱法检测 氟吡菌胺及其代谢物和霜霉威在叶用 莴苣中的残留及消解动态[J]. 农药学学报, 2021, 23(2): 388-394. doi: 10.16801/j.issn.1008-7303.2021.0026
Hongxia TANG, Jiaqing HUANG, Qiang SUN, Guangyue WEN, Maofeng DONG, Weimin WANG. Residue and dissipation of fluopicolide, its metabolite and propamocarb in the leaf lettuce using a modified QuEChERS method and HPLC-MS/MS[J]. Chinese Journal of Pesticide Science, 2021, 23(2): 388-394. doi: 10.16801/j.issn.1008-7303.2021.0026
Citation: Hongxia TANG, Jiaqing HUANG, Qiang SUN, Guangyue WEN, Maofeng DONG, Weimin WANG. Residue and dissipation of fluopicolide, its metabolite and propamocarb in the leaf lettuce using a modified QuEChERS method and HPLC-MS/MS[J]. Chinese Journal of Pesticide Science, 2021, 23(2): 388-394. doi: 10.16801/j.issn.1008-7303.2021.0026

QuEChERS-高效液相色谱-串联质谱法检测 氟吡菌胺及其代谢物和霜霉威在叶用 莴苣中的残留及消解动态

doi: 10.16801/j.issn.1008-7303.2021.0026
基金项目: 上海市科技兴农项目 (2019-02-08-00-12-F01144);小宗作物农药残留评估及膳食风险评价 (农科国推2019 (匹配-34))
详细信息
    作者简介:

    唐红霞,女,硕士研究生,E-mail:lobsterjane@163.com

    通讯作者:

    董茂锋,通信作者 (Author for correspondence),男,副研究员,研究方向为农药残留分析,E-mail:dmf385@163.com

    王伟民,共同通信作者 (Co-author for correspondence),男,研究员,研究方向为农药残留分析和风险评估,E-mail:173915883@qq.com

  • 中图分类号: S482.2;TQ450.263;O657.7

Residue and dissipation of fluopicolide, its metabolite and propamocarb in the leaf lettuce using a modified QuEChERS method and HPLC-MS/MS

  • 摘要: 样品通过改良的QuEChERS方法提取净化,建立了高效液相色谱-串联质谱检测叶用莴苣 Loctuca sativa L. var. ramosa Hort. 中氟吡菌胺及其代谢物2,6-二氯苯甲酰胺和霜霉威残留量的分析方法。样品经乙腈提取,多壁碳纳米管净化,基质匹配标准溶液外标法定量。结果显示:在0.005~1 mg/L范围内,目标化合物的质量浓度与对应的响应值间呈良好线性关系 (R2 ≥ 0.999)。在0.02、0.1、2和100 mg/kg添加水平下,3种化合物在叶用莴苣中的回收率在85%~106%之间,相对标准偏差在1.0%~18%(n = 5) 之间;3种化合物的定量限均为0.02 mg/kg。田间试验结果表明,当687.5 g/L氟菌 • 霜霉威悬浮剂以有效成分928.13 g/hm2施药3次、施药间隔期为7 d时,叶用莴苣中氟吡菌胺和霜霉威的消解动态均符合一级反应动力学方程,半衰期分别为3.9~4.2和4.8~4.9 d。末次施药后5 d和7 d时,氟吡菌胺和霜霉威在叶用莴苣中的残留量分别为3.45~8.51和9.05~31.1 mg/kg,而2,6-二氯苯甲酰胺的残留量均低于定量限 (0.02 mg/kg)。结合中国和国际食品法典委员会 (CAC) 的最大残留限量以及叶用莴苣的生长特点和消费习惯,推荐687.5 g/L氟菌 • 霜霉威悬浮剂在叶用莴苣上施用的安全间隔期为5 d。
  • 1  氟吡菌胺 (A)、2,6-二氯苯甲酰胺 (B) 和霜霉威盐酸盐 (C) 结构式

    1.  The structural formula of fluopicolide (A), 2,6-dichlorobenzamide (B) and propamocarb-hydrochloride (C)

    图  1  不同提取溶剂下霜霉威、氟吡菌胺和2,6-二氯苯甲酰胺在叶用莴苣中的回收率

    Figure  1.  Recoveries of leaf lettuce with propamcarb, fluopicplide and 2,6-dichlorobenzamide using different extraction solvents

    图  2  不同吸附材料的净化效果

    A. 不同吸附材料下的回收率;B. 不同MWCNTs用量下的回收率;C. 不同吸附材料的净化效果;D. 不同MWCNTs用量下的净化效果。

    Figure  2.  Optimization of purification effect with different adsorption materials

    A. Recoveries with different sorbents; B. Recoveries with different mount of MWCNTs; C. Purification by different sorbents; D. Purification by different mount of MWCNTs.

    表  1  霜霉威、氟吡菌胺和2,6-二氯苯甲酰胺质谱条件参数

    Table  1.   Mass spectrometry parameters for propamocarb, fluopicolide and 2,6-dichlorobenzamide

    分析物
    Analyte
    保留时间
    Retention
    time/min
    定量离子对
    Quantitative ion,
    m/z
    定性离子对
    Qulititative ion,
    m/z
    Q1 Pre Bias/V碰撞能量
    Collision
    energy/V
    Q3 Pre Bias/V
    霜霉威 propamocarb 0.935 189.20/102.05 189.20/102.05 −14.0 −18.0 −21.0
    189.20/74.05 −14.0 −28.0 −28.0
    氟吡菌胺 fluopicolide 3.459 383.00/173.00 383.00/173.00 −12.0 −23.0 −30.0
    383.00/144.90 −20.0 −51.0 −26.0
    2,6-二氯苯甲酰胺 2,6-dichlorobenzamide 1.699 190.00/172.95 190.00/172.95 −10.0 −19.0 −30.0
    190.00/145.00 −10.0 −30.0 −25.0
    下载: 导出CSV

    表  2  霜霉威、氟吡菌胺和2,6-二氯苯甲酰胺在叶用莴苣中的添加回收率及相对标准偏差

    Table  2.   The recoveries and RSDs of propamocarb, fluopicolide and 2,6-dichlorobenzamide in leaf lettuce

    分析物
    Analyte
    添加水平
    Spiked level/
    (mg/kg)
    平均
    回收率
    Average
    recovery/%
    相对
    标准偏差
    RSD/%
    校准曲线及决定系数
    Calibration curves and coefficient of
    determination, R2
    基质效应
    Me/%
    定量限
    LOQ/(mg/kg)
    霜霉威 propamocarb 0.02 102 3 y = 11714272x + 49862, R2 = 1.000 64 0.02
    0.1 101 3
    2 102 2
    100* 91 6
    氟吡菌胺 fluopicolide 0.02 106 2 y = 7766323x + 106149, R2 = 0.999 4.3 0.02
    0.1 100 3
    2 101 2
    100* 102 1
    2,6-二氯苯甲酰胺
    2,6-dichlorobenzamide
    0.02 86 18 y = 377216x−1067, R2 = 1.000 21 0.02
    0.1 99 7
    2 99 5
    100* 85 5
    注:*额外稀释50倍进样。Note: * An additional dilution of 50 times.
    下载: 导出CSV

    表  3  霜霉威、氟吡菌胺在叶用莴苣中的消解动态

    Table  3.   Dissipation dynamic of propamocarb, fluopicolide in leaf lettuce

    采样时间
    Sampling time/d
    霜霉威残留量
    propamocarb residue/(mg/kg)
    氟吡菌胺残留量
    fluopicolide residue/(mg/kg)
    奉贤
    Fengxian
    松江
    Songjiang
    奉贤
    Fengxian
    松江
    Songjiang
    0 (2 h) 24.4 57.3 6.55 16.0
    1 22.3 35.4 6.96 10.1
    3 23.5 35.1 7.03 8.62
    5 13.6 31.1 4.88 8.51
    7 9.05 16.5 3.45 3.45
    10 6.65 12.4 1.22 2.48
    消解动力学方程 Dissipation dynamic equation ct = 27.387e−0.142t ct = 51.548e−0.143t ct = 8.891e−0.166t ct = 14.876e−0.179t
    半衰期 Half-life/d 4.9 4.8 4.2 3.9
    下载: 导出CSV

    表  4  霜霉威、氟吡菌胺和2,6-二氯苯甲酰胺在叶用莴苣中的最终残留量

    Table  4.   Terminal residue of propamocarb, fluopicolide and 2,6-dichlorobenzamide in leaf lettuce

    农药
    Pesticide
    采样时间
    Sampling time/d
    残留量
    Residue/(mg/kg)
    奉贤
    Fengxian
    松江
    Songjiang
    霜霉威
    propamocarb
    5 13.6 31.1
    7 9.05 16.5
    氟吡菌胺
    fluopicolide
    5 4.88 8.51
    7 3.45 3.45
    2,6-二氯苯甲酰胺
    2,6-dichlorobenzamide
    5 < 0.02 < 0.02
    7 < 0.02 < 0.02
    下载: 导出CSV
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  • 收稿日期:  2020-06-16
  • 录用日期:  2020-07-24
  • 刊出日期:  2021-04-10

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