液液萃取/气相色谱-串联质谱法测定人尿中16种羟基多环芳烃  

Determination of 16 Hydroxy Polycyclic Aromatic Hydrocarbons in Human Urine by Liquid-Liquid Extraction/Gas Chromatography-Tandem Mass Spectrometry

作　　者：鲍珊 钱柬坤 付慧[1] 邱天[1] 陆一夫[1,3] BAO Shan;QIAN Jian-kun;FU Hui;QIU Tian;LU Yi-fu(China CDC Key Laboratory of Environment and Population Health,National Institute of Environmental Health,Chinese Center for Disease Control and Prevention,Beijing 100021,China;School of Public Health,China Medical University,Shenyang 110122,China;Center for Global Health,School of Public Health,Nanjing Medical University,Nanjing 211166,China)

机构地区：[1]中国疾病预防控制中心环境与人群健康重点实验室,中国疾病预防控制中心环境与健康相关产品安全所,北京100021 [2]中国医科大学公共卫生学院,辽宁沈阳110122 [3]南京医科大学公共卫生学院全球健康中心,江苏南京211166

出　　处：《分析测试学报》2024年第2期261-268,共8页Journal of Instrumental Analysis

基　　金：国家卫生健康委员会公共卫生专项(131031108000160004);国家自然科学基金资助项目(82025030,82222063,82241091)。

摘　　要：建立了同时测定人尿中16种羟基多环芳烃(OH-PAHs)的液液萃取/气相色谱-串联质谱法(LLE/GCMS/MS)。1 mL尿样经β-葡萄糖苷酸酶/硫酸芳酯酶酶解后,使用甲苯和正戊烷(1∶4)混合溶剂重复提取两次,提取液经硝酸银溶液除杂后氮吹浓缩至近干,甲苯复溶后加入N-甲基-N-(三甲基硅烷)三氟乙酰胺(MSTFA)进行衍生化反应后待测。待测物经TG-5SilMS毛细管色谱柱分离,在多反应监测(MRM)模式下以内标法定量。该研究对衍生化反应条件、仪器参数、酶添加量、提取溶剂进行比较和优化,评估了基质效应,并考察了方法的精密度和准确度。结果表明,1-羟基萘(1-NAP)和2-羟基萘(2-NAP)在0.1~100μg/L范围内线性关系良好,其他目标物在0.02~20μg/L范围内线性关系良好,方法检出限为0.01~0.19μg/L,定量下限为0.03~0.62μg/L,加标回收率为81.6%~122%,日内和日间相对标准偏差(RSD)分别为0.22%~5.5%和0.76%~10%,标准参考样品SRM 3672测定结果与参考值的相对偏差均小于10%。应用该方法测定国家人体生物监测项目采集的529份尿样,结果显示除3-羟基屈(3-CHR)外,其他15种OH-PAHs均检出,8种目标物的检出率超过90%。1-NAP和2-NAP的质量浓度水平高于其他组分,中位数分别为1.09μg/L和1.95μg/L。该方法成本低、分离度好、灵敏度高、基质效应干扰小,适用于普通人群尿中OH-PAHs负荷水平的监测。A liquid-liquid extraction gas chromatography-tandem mass spectrometry(LLE/GC-MS/MS)method was established for the simultaneous determination of 16 hydroxy polycyclic aromatic hydrocarbons(OH-PAHs)in human urine.β-glucuronidase/sulfatase was added to 1 mL human urine to release target analytes by an enzymatic hydrolysis reaction.Toluene/n-pentane(1∶4)was used for LLE and repeated this process twice.The extraction solution was further cleaned up using silver nitrate solution.The eluate was evaporated under nitrogen to near-dryness and reconstituted with toluene,then derivatized with N-methyl-N-(trimethylsilyl)trifluoroacetamide(MSTFA).After the derivatization,it was separated by TG-5SilMS capillary chromatography column and quantified using the internal standard method in multi reaction monitoring(MRM)mode.In this study,the derivatization reaction conditions,instrument parameters,addition amount of enzyme,and different extraction solvent were compared and optimized.The matrix effect was evaluated while the accuracy and precision of the method was investigated.The results show that 1-hydroxynaphthalene(1-NAP)and 2-hydroxynaphthalene(2-NAP)had good linearities at 0.1-100μg/L,and other target analytes were 0.02-20μg/L.The method limits of detection were 0.01-0.19μg/L,and the limits of quantitation were 0.03-0.62μg/L.The spiked recoveries were 81.6%-122%,the relative standard deviations of inter-day and intra-day were 0.22%-5.5%and 0.76%-10%,respectively,and the relative deviation between the measured results and the reference value of SRM 3672 was less than 10%.This method was applied to determine 529 urine samples collected from the National Human Biological Monitoring Project.The results showed that a total of 15 OH-PAHs were detected except 3-hydroxychrysene(3-CHR),while 8 compounds had a detection frequency over 90%.The concentrations of 1-NAP and 2-NAP were higher than other components,with median values of 1.09μg/L and 1.95μg/L,respectively.This method is suitable for monitoring human urinary OH-PAHs l

关 键 词：液液萃取 气相色谱-串联质谱 羟基多环芳烃 人尿 

分 类 号：O657.63[理学—分析化学] O625.15[理学—化学]