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[基于QuEChERS-超高效液相色谱-串联质谱法测定水果和蔬菜中的79种农药残留]

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

作者信息

Zhao Le, Liu Xian-Jun, Zhang Hao, Li Jian, Cai Liang, Fan Xiang, Li Tan-Yao, Chen Dong-Yang

机构信息

School of Public Health,University of South China,Hengyang 421001,China.

Hunan Provincial Center for Disease Control and Prevention (Hunan Academy of Preventive Medicine),Changsha 410153,China.

出版信息

Se Pu. 2025 Sep;43(9):1053-1062. doi: 10.3724/SP.J.1123.2025.02015.

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 () 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.

摘要

水果和蔬菜中的农药残留正成为一个严重问题。这些残留会影响农产品质量和人体健康。因此,在食品安全领域有效监测和控制农药残留变得至关重要。本研究建立了一种快速有效的QuEChERS-超高效液相色谱-串联质谱法(QuEChERS-UPLC-MS/MS),用于同时测定蔬菜和水果中的79种典型农药,包括有机磷类、氨基甲酸酯类和拟除虫菊酯类。对预处理、UPLC和MS/MS条件进行了优化。水果和蔬菜样品经粉碎和匀浆后用冷冻乙腈提取,采用QuEChERS方法净化,通过离心膜过滤,然后用UPLC-MS/MS分析。分离在ACQUITY UPLC HSS T3柱(100 mm×2.1 mm,1.8 μm)上进行,采用梯度洗脱。水相和有机相分别为水-甲醇(98∶2,v/v)和甲醇-水(98∶2,v/v),均含有5 mmol/L乙酸铵和0.1%甲酸。采用三重四极杆质谱仪在正离子电喷雾电离(ESI)扫描模式下,使用基质匹配标准曲线法对目标农药残留进行定量。结果表明,在优化条件下,79种目标化合物在0.1 - 200 μg/L范围内线性良好,相关系数()均大于0.990。79种化合物的检出限(LOD)和定量限(LOQ)分别在0.01 - 4.0 μg/kg和0.03 - 13.0 μg/kg范围内。三个加标水平的回收率在78.2%至119.8%之间,相对标准偏差(RSD)均小于15.8%。所建立的方法成功应用于湖南省的80份水果和蔬菜样品。结果,在31份样品中检测到19种农药,其中噻虫嗪、啶虫脒和噻虫胺检出率最高,含量范围为0.012 - 2.62 mg/kg;根据湖南省调查年鉴的数据,计算了所检测的新烟碱类杀虫剂(噻虫嗪和噻虫胺)慢性膳食暴露的每日允许摄入量百分比(%ADI)。结果表明,水果和蔬菜中噻虫胺的%ADI分别在5.74%至0.36%之间,水果和蔬菜中噻虫嗪的%ADI分别在0.40%至19.50%之间。发现两种农药的%ADI均小于100%,表明它们在可接受范围内。该方法简便、灵敏、准确,适用于同时测定水果和蔬菜中的多种农药残留。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/66d4/12412020/b5146633b2fc/F0F92704-9730-45b4-9C54-9A75725C8AB7-F001.jpg

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