摘要
有机磷酸酯(OPEs)广泛应用于日常生活中,环境中的OPEs进入人体后会被迅速代谢产生二酯类代谢物(di-OPEs).本研究建立了同时检测头发中10种OPEs和8种di-OPEs的分析方法,采用高效液相色谱串联质谱(HPLC-MS/MS)进行定性和定量分析. 0.1 g头发样品研磨成粉末后,使用4 mL正己烷/乙酸乙酯/甲醇(1∶1∶1, V/V/V)混合溶液超声萃取3次,随后加入20 mg无水硫酸钠(Na_(2)SO_(4))和100 mg十八烷基硅烷键合硅胶18(C18)进行净化,氮吹浓缩后采用HPLC-MS/MS检测.色谱流动相为甲醇和0.01 mol·L^(-1)乙酸铵水溶液,离子扫描采用正负切换模式.在优化的实验条件下,OPEs和di-OPEs在0.2—500 ng·mL^(-1)范围内均表现出良好的线性关系(R^(2) >0.995).头发样品中10种OPEs加标回收率平均值介于60.3%—128%之间,相对标准偏差RSD为0.6%—19.8%;8种di-OPEs平均加标回收率为60.7%—125%,RSD介于1.43%—17.5%之间. OPEs和di-OPEs的方法检出限分别为0.08—6.59 ng·g^(-1)和0.23—5.42 ng·g^(-1).使用该方法对18份头发样品中的OPEs和di-OPEs含量进行定量分析,结果显示10种OPEs的中位浓度介于未检出(nd)—27.3 ng·g^(-1)之间,其中磷酸三苯酯(TPHP)、磷酸三(2-氯丙基)酯(TCPP)和磷酸三(2-丁氧乙基)酯(TBOEP)在所有样品中均有检出.8种di-OPEs的中位浓度范围为nd—38.4 ng·g^(-1),最常见的化合物为磷酸二苯酯(DPHP)、双(1,3-二氯-2-丙基)磷酸酯(BDCPP)和磷酸二丁酯(DBP),检出率均为100%.本方法为综合评估人体内OPEs和di-OPEs的暴露水平提供了可靠的技术支持.
Organophosphate esters(OPEs)are widely used in daily life and can be rapidly metabolized into diester metabolites(di-OPEs)upon entering the human body.An effective method was developed for the analysis of 10 OPEs and 8 di-OPEs in hair using high performance liquid chromatography-tandem mass spectrometry(HPLC-MS/MS).After pulverization,0.1 g of hair powder was sonicated with 4 mL of a n-hexane/ethyl acetate/methanol mixture(1:1:1,V/V/V)for three times.The organic phase was then purified using 100 mg of C18(octadecyl bonded silica)and 20 mg of anhydrous sodium sulfate.The supernatant was concentrated by nitrogen flow and subsequently analyzed by HPLC-MS/MS.The chromatographic mobile phase consisted of methanol and 0.01 mol·L^(-1) ammonium acetate aqueous solution.Ion scanning was performed in both positive and negative ion modes.Under the optimized conditions,both OPEs and di-OPEs showed good linearities in the 0.2—500 ng·mL-1 concentration range(R^(2)>0.995).The average recoveries of OPEs in hair ranged from 60.3%to 128%,with RSD values ranging from 0.6%—19.8%,while those of di-OPEs ranged from 60.7%to 125%,with RSD values ranging from 1.43%—17.5%.The detection limits of OPEs and di-OPEs were 0.08—6.59 ng·g^(-1) and 0.23—5.42 ng·g^(-1),respectively.This method was used to determine OPEs and di-OPEs in 18 hair samples.Results showed that the median concentrations of 10 OPEs ranged from nd to 27.3 ng·g^(-1),and triphenyl phosphate(TPHP),tris(2-chloropropyl)phosphate(TCPP),and tris(2-butoxyethyl)phosphate(TBOEP)were detected in all samples.The median concentrations of 8 di-OPEs ranged from nd to 38.4 ng·g^(-1),and the detection frequencies of diphenyl phosphate(DPHP),bis(1,3-dichloro-2-propyl)phosphate(BDCPP),and dibutyl phosphate(DBP)were 100%.Our method provides reliable technical support for the comprehensive assessment of OPEs and di-OPEs exposure levels in humans.
作者
秦瑞欣
张释义
李丽
高浪琴
黄璐璐
蔡凤珊
廖其龙
彭先芝
郑晶
QIN Ruixin;ZHANG Shiyi;LI Li;GAO Langqin;HUANG Lulu;CAI Fengshan;LIAO Qilong;PENG Xianzhi;ZHENG Jing(State Key Laboratory of Advanced Environmental Technology,Guangzhou Institute of Geochemistry,Chinese Academy of Sciences,Guangzhou,510640,China;The Key Laboratory of Environmental Pollution Health Risk Assessment,Research Center of Emerging Contaminants,South China Institute of Environmental Sciences,Ministry of Ecology and Environment,Guangzhou,510655,China;The Key Laboratory of Environmental Pollution Monitoring and Disease Control,Ministry of Education,School of Public Health and Wellness,Guizhou Medical University,Guiyang,550025,China;University of Chinese Academy of Sciences,Beijing,100049,China)
出处
《环境化学》
2026年第2期789-799,共11页
Environmental Chemistry
基金
国家自然科学基金(42222711,42077404)
广州市科技计划项目(202206010061)
中央级公益性科研院所基本科研业务费专项资金(PM-zx097-202305-247)资助。
关键词
有机磷酸酯
代谢产物
头发
高效液相色谱串联质谱
分析方法
organophosphate esters
metabolites
hair
high liquid chromatography tandem mass spectrometry
analytical method
