固相萃取-超高效液相色谱-三重四极杆质谱法同时测定不同水体中的6种雌激素

Simultaneous determination of six estrogens in different water bodies bysolid phase extraction and ultra performance liquid chromatographycoupled with triple quadrupole mass spectrometry

建立了固相萃取-超高效液相色谱-三重四极杆质谱(SPE-UPLC-MS/MS)联用技术同时测定不同水体中6种雌激素(雌三醇、17-β-雌二醇、17-α-雌二醇、雌酮、炔雌醇、己烯雌酚)的分析方法。样品经HLB固相萃取柱提取和净化后经BEH C18色谱柱分离,采用MS/MS多反应监测模式(MRM)进行分析。采用内标法定量,以雌三醇-D3、17-β-雌二醇-D2、己烯雌酚-D8为内标。当6种雌激素的质量浓度在1.0~100μg/L线性范围内时,所得回归方程的相关系数(r)均不小于0.998 2;方法检出限为0.27~0.45 ng/L,定量限为1.08~1.78 ng/L;在高、中、低3个添加水平下的回收率为68.3%~97.4%,相对标准偏差(RSD)小于15%。该方法灵敏、准确,检测范围广,分析速度快,适用于地表水、废水、饮用水源水及生活用水等不同水体中6种雌激素的同时检测。

Abstract： A method has been developed for the simultaneous determination of six estrogens （estriol, 17-fl-estradiol, 17-a-estradiol, estrone, ethinyloestradiol, diethylstilbestrol） in water environment by solid phase extraction and ultra performance liquid chromatography couple with triple quadrupole mass spectrometry. After enriched and purified by an HLB solid phase extrac- tion column, the six estrogens were separated by a BEH C18 column and then determined by MS/MS with multiple reaction monitoring （MRM） mode. The quantification was achieved by internal standard method, with estriol-D3, estradiol-D2 and diethylstilbestrol-D8 as the internal standards. Good linear relationships were obtained in the mass concentration range of ｜. 0 - 100 p^g/L with high correlation coefficients over 0.998 2. The limits of detection and quantification for the six estrogens were 0.27 -0.45 ng/L and I. 08 - I. 78 ng/L, respectively. The recoveries were in the range of 68.3% - 97.4% at the three spiked levels and with the relative standard deviations below 15%. The method shows high sensitivity, good precision, extensive analytical range and high analytical speed. It was successfully applied to the simultaneous detection of the six estrogens in four different water bodies including surface water, waste water, source water of drinking and domestic water.