陈玉婕, 邓淑铃, 周永林, 张昊, 刘华良. 液相色谱-串联质谱法检测人体尿液中12种农药代谢物[J]. 环境与职业医学, 2024, 41(8): 919-924, 953. DOI: 10.11836/JEOM24028
引用本文: 陈玉婕, 邓淑铃, 周永林, 张昊, 刘华良. 液相色谱-串联质谱法检测人体尿液中12种农药代谢物[J]. 环境与职业医学, 2024, 41(8): 919-924, 953. DOI: 10.11836/JEOM24028
CHEN Yujie, DENG Shuling, ZHOU Yonglin, ZHANG Hao, LIU Hualiang. Determination of 12 pesticide metabolites in human urine by liquid chromatography-tandem mass spectrometry[J]. Journal of Environmental and Occupational Medicine, 2024, 41(8): 919-924, 953. DOI: 10.11836/JEOM24028
Citation: CHEN Yujie, DENG Shuling, ZHOU Yonglin, ZHANG Hao, LIU Hualiang. Determination of 12 pesticide metabolites in human urine by liquid chromatography-tandem mass spectrometry[J]. Journal of Environmental and Occupational Medicine, 2024, 41(8): 919-924, 953. DOI: 10.11836/JEOM24028

液相色谱-串联质谱法检测人体尿液中12种农药代谢物

Determination of 12 pesticide metabolites in human urine by liquid chromatography-tandem mass spectrometry

  • 摘要:
    背景 有机磷和拟除虫菊酯等农药应用广泛,环境介质和食品摄入等多途径暴露所导致的人体健康危害不容忽视,有必要基于农药暴露生物标记进行人体内暴露研究,以客观评估人体农药暴露情况。
    目的 建立快速、准确测定尿液中12种农药代谢物(5种有机磷农药代谢物、4种拟除虫菊酯农药代谢物、2种苯氧乙酸除草剂和1种杀虫剂)的液相色谱-串联质谱法检测方法。
    方法 将尿液样品酶解过夜后,经Oasis HLB 96孔固相萃取提取净化,液相色谱-串联质谱法检测,同位素内标法定量。应用建立的方法检测143份普通人群的尿液样品,考察方法的适用性和了解农药的暴露情况。
    结果 12种目标物均具有良好的线性范围,校准曲线相关系数均大于0.999;方法检出限为0.02~0.19 μg·L−1,方法定量限为0.06~0.27 μg·L−1 。在低、中、高3个浓度加标水平下,方法的回收率在84%~112%之间,日内精密度为0.43%~9.6%,日间精密度为1.6%~9.7%。基于本方法,测定了143份江苏地区的尿液样品,除N,N-二乙基甲苯胺(DEET)外的其他11种农药均有检出。
    结论 本研究建立的固相萃取-液相色谱-串联质谱法,具有检出限低、重复性好、通量高的特点,适用于大批量人体尿液样品中12种农药暴露的定量检测,可为农药的内暴露监测和健康风险评估提供技术支撑。

     

    Abstract:
    Background Pesticides like organophosphorus and pyrethroids are extensively utilized, and associated potential human health risks arising from multi-route exposure, including environmental sources and dietary intake, cannot be overlooked. Conducting human exposure studies using pesticide exposure biomarkers is essential for an objective evaluation of human pesticide exposure levels.
    Objective To develop a rapid and precise liquid chromatography-tandem mass spectrometry method for the detection of 12 pesticide metabolites in urine, including 5 metabolites of organophosphorus pesticide, 4 metabolites of pyrethroid pesticide, 2 metabolites of herbicides, and 1 metabolite of insecticide.
    Methods After overnight enzymatic hydrolysis, urine samples were subjected to extraction and purification using Oasis HLB 96-well solid-phase extraction. Subsequently, the samples were analyzed by liquid chromatography-tandem mass spectrometry and quantified using the isotope internal standard method. The developed method was employed to analyze 143 urine samples from a general population to assess its effectiveness and to evaluate pesticide exposure levels.
    Results All 12 target compounds exhibited good linear ranges, with their correlation coefficients of calibration curves exceeding 0.999. The limits of detection (LOD) ranged from 0.02 to 0.19 μg·L−1, while the limits of quantitation (LOQ) ranged from 0.06 to 0.27 μg·L−1. The recoveries at three spiked levels ranged from 84% to 112%, and the inter- and intra- day precisions of targeted analystes were 0.43%-9.6% and 1.6%-9.7% respectively. Using this method, 143 urine samples from residents in Jiangsu region were analyzed, and 11 pesticides were detected except N,N-diethyl-m-toluamide (DEET).
    Conclusion The established method of solid-phase extraction combined with liquid chromatography-tandem mass spectrometry has the characteristics of low detection limit, good repeatability, and high throughput, which is suitable for quantitative detection of selected 12 pesticides in large batches of human urine samples, and provides technical support for pesticide internal exposure monitoring and health risk assessment.

     

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