色谱

色谱 ›› 2025, Vol. 43 ›› Issue (9): 1053-1062.DOI: 10.3724/SP.J.1123.2025.02015

• 研究论文 • 上一篇    下一篇

QuEChERS-超高效液相色谱-串联质谱法测定果蔬中79种农药残留

赵乐1, 刘先军2, 张昊2, 李剑2, 蔡亮2, 范翔2, 李谭瑶2, 陈东洋1,2,*()   

  1. 1.南华大学公共卫生学院，湖南 衡阳 421001
    2.湖南省疾病预防控制中心（湖南省预防医学科学院），湖南 长沙 410153
  • 收稿日期:2025-02-26 出版日期:2025-09-08 发布日期:2025-09-04
  • 通讯作者: *Tel：（0731）84305950，E-mail：dychen2008@126.com.
  • 基金资助:
    湖南省自然科学基金(2021JJ70085);湖南省自然科学基金(2025JJ80673);湖南省卫生健康高层次人才支持计划(20240304107);湖南省卫生健康高层次人才支持计划(20240304043);湖南省卫生健康委科研项目(B20160073);湖南省卫生健康委科研项目(C20191035);湖南省卫生健康委科研项目(D202312069311)

Determination of 79 pesticide residues in fruits and vegetables by QuEChERS-ultra performance liquid chromatography-tandem mass spectrometry

ZHAO Le1, LIU Xianjun2, ZHANG Hao2, LI Jian2, CAI Liang2, FAN Xiang2, LI Tanyao2, CHEN Dongyang1,2,*()   

  1. 1. School of Public Health，University of South China，Hengyang 421001，China
    2. Hunan Provincial Center for Disease Control and Prevention （Hunan Academy of Preventive Medicine），Changsha 410153，China
  • Received:2025-02-26 Online:2025-09-08 Published:2025-09-04
  • Supported by:
    Hunan Provincial Natural Science Foundation(2021JJ70085);Hunan Provincial Natural Science Foundation(2025JJ80673);Hunan Provincial Health High-Level Talent Support Program(20240304107);Hunan Provincial Health High-Level Talent Support Program(20240304043);Research Project of Health Commission of Hunan Province(B20160073);Research Project of Health Commission of Hunan Province(C20191035);Research Project of Health Commission of Hunan Province(D202312069311)

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摘要：

果蔬中农药残留是影响农产品质量和消费者身体健康的热点问题，如何有效监测和控制农药残留已成为食品安全领域的重要课题。通过优化QuEChERS前处理方法及仪器测定参数，建立了果蔬中有机磷类、氨基甲酸酯类、拟除虫菊酯类等79种典型农药的QuEChERS-超高效液相色谱-串联质谱（QuEChERS-UPLC-MS/MS）同时测定方法。果蔬样品经均质后在4 ℃条件下用乙腈提取，QuEChERS法净化并离心过滤后进行UPLC-MS/MS分析。采用ACQUITY UPLC HSS T3（100 mm×2.1 mm，1.8 μm）色谱柱分离，以水-甲醇（98∶2，v/v，含5 mmol/L乙酸铵和0.1%甲酸）为水相，甲醇-水（98∶2，v/v，含5 mmol/L乙酸铵和0.1%甲酸）为有机相进行梯度洗脱。采用三重四极杆质谱仪，在电喷雾离子源正离子扫描模式下，基质匹配标准曲线法定量。结果表明，在优化的条件下，目标化合物在0.1~200 μg/L范围内线性关系良好，相关系数（r）均大于0.990；79种化合物的检出限（LOD）和定量限（LOQ）范围分别为0.01~4.0 μg/kg和0.03~13.0 μg/kg，3个添加水平下回收率为 78.2%~119.8%，相对标准偏差（RSD）均小于15.8%。采用建立的方法对80份果蔬样本进行检测，31份样本中检出19种农药，以噻虫胺、啶虫脒和噻虫嗪检出率最高，含量为0.012~2.62 mg/kg；对检出的烟碱类农药（噻虫胺和噻虫嗪）进行了初步风险评估，结果显示，噻虫胺在水果和蔬菜中的慢性膳食摄入风险值（%ADI）分别为5.74%和0.36%，噻虫嗪在水果和蔬菜中的%ADI分别为0.40%、19.50%，二者在蔬菜和水果中的%ADI均低于100%，均在可接受范围内。该方法简便、灵敏、准确，适用于果蔬中多种农药残留的同时测定。

关键词: 农药残留, 超高效液相色谱-串联质谱法, QuEChERS, 风险评估

Abstract:

Pesticide residues in fruits and vegetables are becoming a serious issue. These residues can affect the quality of agricultural products and people’s health. Therefore， it has become crucial to effectively monitor and control pesticide residues in the food safety field. In this study， a rapid and effective QuEChERS-ultra performance liquid chromatography-tandem mass spectrometry （QuEChERS-UPLC-MS/MS） method was established for the simultaneous determination of 79 typical pesticides in vegetables and fruits， including organophosphates， carbamates， and pyrethroids. The pretreatment， UPLC， and MS/MS conditions were optimized. The fruit and vegetable samples were extracted with frozen acetonitrile after pulverization and homogenization， cleaned up by the QuEChERS method， filtered through a centrifugal membrane， and analyzed by UPLC-MS/MS. The separation was carried out on an ACQUITY UPLC HSS T3 column （100 mm×2.1 mm， 1.8 μm） with gradient elution. The aqueous and organic phases were water-methanol （98∶2， v/v） and methanol-water （98∶2， v/v） respectively， both with 5 mmol/L ammonium acetate and 0.1% formic acid. A triple quadrupole mass spectrometer was used in positive-ion electrospray ionization （ESI+） scanning mode， with target pesticide residues quantified using the matrix-matched standard-curve method. The results showed that under the optimized conditions， the 79 target compounds were determined with good linearities in the range of 0.1-200 μg/L， and the correlation coefficients （r） were all greater than 0.990. The limits of detection （LODs） and limits of quantification （LOQs） of the 79 compounds were in the range of 0.01-4.0 μg/kg and 0.03-13.0 μg/kg. The recoveries at three spiked levels ranged from 78.2% to 119.8%， with relative standard deviations （RSDs） all less than 15.8%. The established method was successfully applied to 80 samples of fruits and vegetables from Hunan province. As a result， 19 pesticides were detected in 31 samples， and thiamethoxam， acetamiprid and clothianidin being the most highly detected with a content range of 0.012-2.62 mg/kg； According to the data of the Hunan province survey yearbook， the percentages of acceptable daily intake （%ADI） for chronic dietary exposure of the detected neonicotinoid insecticides （thiamethoxam and clothianidin） have been calculated. The results indicate that the %ADI of clothianidin in fruits and vegetables ranged from 5.74% to 0.36%， respectively， and the %ADI of thiamethoxam in fruits and vegetables ranged from 0.40% to 19.50%. The %ADI of both pesticides were found to be less than 100%， indicating they are within acceptable limits. The method is simple， sensitive， accurate， and suitable for the simultaneous determination of multiple pesticide residues in fruits and vegetables.

Key words: pesticide residues, ultra performance liquid chromatography-tandem mass spectrometry （UPLC-MS/MS）, QuEChERS, risk assessment

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