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

作　　者：陈玉婕 邓淑铃 周永林 张昊 刘华良 CHEN Yujie;DENG Shuling;ZHOU Yonglin;ZHANG Hao;LIU Hualiang(School of Public Health,Nanjing Medical University,Nanjing,Jiangsu 211100,China;Department of Physical and Chemical Inspection,Jiangsu Provincial Center for Disease Control and Prevention,Nanjing,Jiangsu 210009,China)

机构地区：[1]南京医科大学公共卫生学院,江苏南京211100 [2]江苏省疾病预防与控制中心理化检验所,江苏南京210009

出　　处：《环境与职业医学》2024年第8期919-924,953,共7页Journal of Environmental and Occupational Medicine

基　　金：江苏省重点研发计划(社会发展)项目(BE2021740)。

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0.02~0.19μg·L^(-1),方法定量限为0.06~0.27μg·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。[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 0.19μg·L^(-1),while the limits of quantitation(LOQ)ranged from 0.06 to 0.27μg·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 sampl

关 键 词：农药代谢物 液相色谱-串联质谱法 尿液 人体生物监测 内暴露 

分 类 号：R11[医药卫生—公共卫生与预防医学]