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改进的QuEChERS-高效液相色谱-串联质谱法同时测定蔬菜水果中百菌清及其代谢物残留

毕瑞锋 邓锁成 付萌 张伟伟 张义霞

毕瑞锋, 邓锁成, 付萌, 张伟伟, 张义霞. 改进的QuEChERS-高效液相色谱-串联质谱法同时测定蔬菜水果中百菌清及其代谢物残留[J]. 农药学学报, 2022, 24(2): 429-434. doi: 10.16801/j.issn.1008-7303.2021.0161
引用本文: 毕瑞锋, 邓锁成, 付萌, 张伟伟, 张义霞. 改进的QuEChERS-高效液相色谱-串联质谱法同时测定蔬菜水果中百菌清及其代谢物残留[J]. 农药学学报, 2022, 24(2): 429-434. doi: 10.16801/j.issn.1008-7303.2021.0161
BI Ruifeng, DENG Suocheng, FU Meng, ZHANG Weiwei, ZHANG Yixia. Simultaneous determination of chlorothalonil and its metabolite in fruits and vegetables using modified QuEChERS-high performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Pesticide Science, 2022, 24(2): 429-434. doi: 10.16801/j.issn.1008-7303.2021.0161
Citation: BI Ruifeng, DENG Suocheng, FU Meng, ZHANG Weiwei, ZHANG Yixia. Simultaneous determination of chlorothalonil and its metabolite in fruits and vegetables using modified QuEChERS-high performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Pesticide Science, 2022, 24(2): 429-434. doi: 10.16801/j.issn.1008-7303.2021.0161

改进的QuEChERS-高效液相色谱-串联质谱法同时测定蔬菜水果中百菌清及其代谢物残留

doi: 10.16801/j.issn.1008-7303.2021.0161
详细信息
    通讯作者:

    毕瑞锋,prefers@163.com.

  • 中图分类号: O657.63;X592

Simultaneous determination of chlorothalonil and its metabolite in fruits and vegetables using modified QuEChERS-high performance liquid chromatography-tandem mass spectrometry

  • 摘要: 建立了同时检测蔬菜水果中百菌清及其代谢物4-羟基百菌清的高效液相色谱-串联质谱分析方法。样品经酸化乙腈提取后,采用配备大气压化学电离源的三重四极杆串联质谱仪测定。结果表明:百菌清及其代谢物4-羟基百菌清在0.005~0.2 mg/L范围内峰面积与质量浓度的线性关系良好,决定系数(R2)大于0.99;方法定量限为0.01 mg/kg。在0.01、0.05和0.2 mg/kg 3个添加水平下,百菌清及其代谢物4-羟基百菌清在结球甘蓝、黄瓜、葡萄和苹果4种基质空白样品中的平均回收率为83%~104%,相对标准偏差(RSD)为 0.73%~7.7% (n=6)。该方法简单快速、准确可靠,适合蔬菜水果中百菌清及其代谢物4-羟基百菌清的定量测定。
  • 图  1  百菌清及其代谢物的MRM色谱图

    Figure  1.  MRM chromatogram of chlorothalonil and its metabolite

    图  2  酸度调节剂对目标分析物回收率的影响

    1. No acidity regulator;2. 0.1 mL HAc + 1.5 g NaAc; 3. 0.1 mL 10% H2SO4; 4. 0.5 mL 10% H2SO4; 5. 1 mL 10% H2SO4; 6. 0.1 mL 10% H3PO4; 7. 0.5 mL 10% H3PO4; 8. 1 mL 10% H3PO4.

    Figure  2.  Effect of acid regulators on the recoveries of the target analytes

    表  1  百菌清及其代谢物的质谱参数

    Table  1.   Mass parameters of chlorothalonil and its metabolite

    化合物
    Compound
    分子式
    Molecular formula
    母离子
    Precursor ion, m/z
    子离子
    Product ion, m/z
    去簇电压
    DP/V
    碰撞能量
    CE/eV
    碎片离子归属
    Classification of
    fragment ion
    百菌清 C8Cl4N2 244.9 181.9* −100 −40 [M−Cl+O−Cl−CO]
    chlorothalonil 174.9 −100 −38 [M−Cl+O−2Cl]
    209.9 −100 −32 [M−Cl+O−Cl]
    146.9 −100 −51 [M−Cl+O−2Cl−CO]
    4-羟基百菌清 C8HCl3N2O 244.9 181.9* −100 −40 [M−H−Cl−CO]
    chlorothalonil-4-hydroxy 174.9 −100 −38 [M−H−2Cl]
    209.9 −100 −32 [M−H−Cl]
    146.9 −100 −51 [M−H−2Cl−CO]
    注 (Note) :*定量离子 (Quantitative ion)。
    下载: 导出CSV

    表  2  百菌清及其代谢物的线性方程、线性范围、决定系数和定量限

    Table  2.   Linear equations, linear ranges, R2 and LOQs for chlorothalonil and its metabolite

    化合物
    Compound
    线性方程
    Linear equation
    线性范围
    Linear range/(mg/L)
    决定系数
    R2
    定量限
    LOQ/(mg/kg)
    百菌清 chlorothalonil y=230804.3x − 12.7 0.005~0.2 0.9985 0.01
    4-羟基百菌清 chlorothalonil-4-hydroxy y=397812.7x + 3.5 0.005~0.2 0.9990 0.01
    下载: 导出CSV

    表  3  百菌清及其代谢物在4种基质中的添加回收率和相对标准偏差 (n=6)

    Table  3.   Recoveries and RSDs of chlorothalonil and its metabolite spiked in the four matrices (n=6)

    基质
    Matrix
    添加水平
    Spiked
    level/
    (mg/kg)
    百菌清
    chlorothalonil
    4-羟基百菌清
    chlorothalonil-4-hydroxy
    平均
    回收率
    Average
    recovery/%
    相对标准
    偏差
    RSD/%
    平均
    回收率
    Average
    recovery/%
    相对标准
    偏差
    RSD/%
    结球甘蓝
    Cabbage
    0.01 104 6.1 95 3.5
    0.05 94 2.3 85 2.5
    0.2 89 2.3 83 3.0
    黄瓜
    Cucumber
    0.01 101 5.9 103 7.7
    0.05 99 4.6 100 2.9
    0.2 94 7.5 91 6.8
    葡萄
    Grape
    0.01 93 3.5 95 3.7
    0.05 95 1.0 90 1.6
    0.2 88 1.3 87 0.73
    苹果
    Apple
    0.01 83 2.6 100 4.2
    0.05 85 3.9 104 2.9
    0.2 84 3.9 103 4.6
    下载: 导出CSV
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  • 收稿日期:  2021-08-10
  • 录用日期:  2021-09-22
  • 网络出版日期:  2021-10-26
  • 刊出日期:  2022-04-01

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