液液萃取-高分辨气相色谱-高分辨双聚焦磁质谱法测定尿中羟基多环芳烃代谢物  

Determination of polycyclic aromatic hydrocarbon metabolites in urine by liquid-liquid extraction-high resolution gas chromatography-high resolution dual-focus magnetic mass spectrometry

作　　者：付慧[1] 陆一夫[1] 胡小键[1] 张续[1] 杨艳伟[1] 朱英[1] FU Hui;LU Yifu;HU Xiaojian;ZHANG Xu;YANG Yanwei;ZHU Ying(National Institute of Environmental Health, Chinese Center for Disease Control and Prevention, Beijing 100021, China)

机构地区：[1]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

出　　处：《色谱》2020年第6期715-721,共7页Chinese Journal of Chromatography

基　　金：中央财政经费项目(131031108000150003).

摘　　要：建立了灵敏、准确的液液萃取-高分辨气相色谱-高分辨双聚焦磁质谱(LLC-HRGC-HRMS)同时测定人体尿样中8种多环芳烃(PAHs)代谢物的方法。将2 mL尿液与氘或13C标记的同位素内标物进行混合,在抗坏血酸的存在下酶解偶联目标物,再将游离化合物用甲苯-戊烷(1∶4,v/v)萃取后浓缩至近干,再用甲苯复溶,衍生后经HRGC-HRMS分离和测定。1-羟基萘在0.14~41.6μg/L、1-羟基菲在0.05~8.33μg/L、2-羟基菲在0.04~8.33μg/L、其他5种代谢产物在0.02~8.33μg/L范围内线性关系良好,相关系数>0.99,方法的检出限为0.006~0.042μg/L,平均回收率为81.4%~127.0%,日内和日间精密度分别为2.7%~6.9%和5.1%~10.9%(n=6)。应用该方法测定330份人群尿液样本,3-羟基?和6-羟基?未检出,其他6种PAHs代谢物检出率为100%。该方法灵敏、准确、稳定,适用于人尿中8种PAHs代谢物的定量分析。A sensitive and accurate method was developed to quantify eight polycyclic aromatic hydrocarbon(PAH)metabolites in human urine by liquid-liquid extraction-high resolution gas chromatography-high resolution dual-focus magnetic mass spectrometry(LLC-HRGC-HRMS).About 2 mL urine was mixed with a deuterium-or 13C-labeled isotopic internal standard,and the conjugated targets were enzymatically digested in the presence of ascorbic acid.The free compounds were extracted with toluene-pentane(1∶4,v/v)and condensed to near dryness.Then,the target compounds were redissolved in toluene.After derivatization,they were separated and quantified by HRGC-HRMS.The linear ranges of the 1-hydroxynaphthalene,1-hydroxyphenanthrene,and 2-hydroxyphenanthrene were 0.14-41.6μg/L,0.05-8.33μg/L,and 0.04-8.33μg/L,respectively,and those for the other five PAH metabolites were 0.02-8.33μg/L.The correlation coefficients were greater than 0.99.The limits of detection were in the range of 0.006-0.042μg/L,and the recoveries were 81.4%-127.0%.The intra-day and inter-day relative standard deviations(RSDs)were less than 6.9%and 10.9%,respectively.This method was utilized for the determination of 330 human urine samples.The results showed that 3-hydroxychrysene and 6-hydroxychrysene were not detected,and the detection rate of the other six PAH metabolites was 100%.This method is sensitive,accurate and stable,and it is suitable for the determination of the eight PAH metabolites in human urine.

关 键 词：高分辨气相色谱-高分辨双聚焦磁质谱 液液萃取 生物监测 羟基多环芳烃代谢物 尿 

分 类 号：O658[理学—分析化学]