人体血清中的多溴联苯醚、邻苯二甲酸酯和双酚A的连续在线分离及气相色谱-质谱测定

Consecutive On-line Separation and Determination of Polybrominated Diphenyl Ethers,Phthalate Esters and Bisphenol A in Human Serum by Gas Chromatography-Mass Spectrometry

建立了人体血清中多种环境雌激素:多溴联苯醚、邻苯二甲酸酯和双酚A的快速可靠的连续在线分离及在气相色谱-质谱上的分析方法。血清样品经过浓盐酸使蛋白质变性,用乙醚萃取,经硅胶柱分离出多个族组分:多溴联苯醚(Polybrominated diphenyl ethers,PBDEs)、邻苯二甲酸酯(Phthalate esters,PAEs)和双酚A(Bisphenol A,BPA),最后由气相色谱-质谱的选择离子检测测定。PBDEs,PAEs和BPA标准曲线回归方程拟合度R2均大于0.99,表明在测试的浓度范围内线性关系良好。PBDEs目标化合物的检出限为0.005～0.048μg/L,PAEs目标化合物的检出限为0.103～0.833μg/L,BPA的检出限是0.035μg/L。标准样品重复样中,PBDEs的RSD(relative standard deviation)值分别为2.8%～10.9%;PAEs的RSD值为5.6%～9.9%;BPA的RSD值为3.0%。实际血清样品中,PBDEs的加标回收物PCB209(Polychloride diphenyl ether 209)的回收率范围是74.8%～88.5%;PAEs中的加标回收物DBP-D4(Dibutyl phthalate-Deutorium 4)的回收率范围为78.7%～97.0%;BPA中的加标回收物BPA-D16(Bisphenol A-Deutorium 16)的回收率范围是76.3%～93.1%。本方法检测血液中多种环境雌激素灵敏度高、重现性和回收率均良好。

An efficient analytical method was established for the consecutive on-line separation of environmental estrogens in human serum,polybrominated diphenyl ethers（PBDEs）,phthalate esters（PAEs） and bisphenol A（BPA） by gas chromatography-mass spectrometry（GC-MS）.After denaturation of protein by concentrated hydrochloride acid,extraction by ether,separation by silica flash chromatographic column,several group components including PBDEs,PAEs and BPA in human serum were separated and purified.Then these components were detected by GC-MS in selected ion monitoring mode.The standard calibration curves of PBDEs,PAEs and BPA were linear over the assayed range with correlation coefficients equal or higher than 0.99.The detected limitations for the targeted compounds ranged from 0.005-0.05 μg/L for PBDEs,0.10-0.83 μg/L for PAEs,and 0.04 μg/L for BPA.In standard duplicated samples,the relative standard deviations were 2.8%-10.9% for PBDEs,5.6%-9.9% for PAEs,and 3.0% for BPA.The surrogate recoveries in these 7 samples ranged from 74.8% to 88.5% for PCB209（polychloride diphenyl ether 209） in PBDEs,from78.7% to 97.0% for DBP-D4（Dibutyl phthalate-Deutorium 4） in PAEs,and from 76.3% to 93.1% for BPA-D16（Bisphenol A-Deutorium 16） in BPA,respectively.This method for detecting multiple environmental estrogens in human serum is sensitive,high reproducible with satisfied recoveries.