Li Yejin, Yang Linyan, Zhen Huajun, Chen Xueming, Sheng Mei, Li Kai, Xue Weibo, Zhao Huihui, Meng Shujuan, Cao Guomin
School of Resources and Environmental Engineering, East China University of Science and Technology, Shanghai 200237, China.
School of Resources and Environmental Engineering, East China University of Science and Technology, Shanghai 200237, China; Shanghai Institute of Pollution Control and Ecological Security, Shanghai 200092, China; National Engineering Laboratory for Industrial Wastewater Treatment, East China University of Science and Technology, Shanghai 200237, China.
J Chromatogr B Analyt Technol Biomed Life Sci. 2021 Apr 1;1168:122559. doi: 10.1016/j.jchromb.2021.122559. Epub 2021 Jan 20.
An analytical method has been developed and validated for the determination of six estrogens and estrogen mimics, namely estriol (E3), bisphenol A (BPA), 17β-estradiol (E2), estrone (E1), ethynyl estradiol (EE2) and dienestrol (DIE), with frequent occurrence in the natural environment. Solid phase extraction coupled with liquid chromatography tandem mass spectrometry (SPE-LC-MS/MS) using electrospray ionization (ESI) in a negative mode was applied to concentration, identification, and quantification of estrogens and estrogen mimics. The SPE conditions were optimized as the selection of C18 as cartridges and MeOH as an eluent, and the control of solution pH at 9.0. The method was validated by satisfactory recoveries (80-130%) and intra-day and inter-day precision (<18.4%, as relative standard deviation), and excellent linearity for calibration curves (R > 0.996). The limits of detection (LODs) for six target estrogenic compounds ranged between 2.5 and 19.2 ng/L. The effects of matrix background on the determination were evaluated in terms of LODs, LOQs, analyte recovery, and slopes of calibration curves in five different water matrices. Matrix effects by tap water were negligible. However, both matrix suppression and enhancement (i.e., E3, E1, DIE) were observed in surface water and wastewater. The positive correlation between LODs and TOC in various water matrices indicated the negative effect of organic pollutants on the method sensitivity. The sum of target estrogenic compounds in environmental samples were within 17-9462 ng/L.
已开发并验证了一种分析方法，用于测定天然环境中经常出现的六种雌激素和雌激素模拟物，即雌三醇（E3）、双酚A（BPA）、17β-雌二醇（E2）、雌酮（E1）、乙炔雌二醇（EE2）和己烯雌酚（DIE）。采用电喷雾电离（ESI）负离子模式的固相萃取-液相色谱串联质谱法（SPE-LC-MS/MS）对雌激素和雌激素模拟物进行富集、鉴定和定量。优化后的SPE条件为选用C18柱作为萃取柱，甲醇作为洗脱剂，并将溶液pH值控制在9.0。该方法通过令人满意的回收率（80%-130%）、日内和日间精密度（相对标准偏差<18.4%）以及校准曲线的良好线性（R>0.996）得到验证。六种目标雌激素化合物的检测限（LOD）在2.5至19.2 ng/L之间。通过在五种不同水基质中评估检测限、定量限、分析物回收率和校准曲线斜率，评价了基质背景对测定的影响。自来水的基质效应可忽略不计。然而，在地表水和废水中均观察到了基质抑制和增强作用（即E3、E1、DIE）。各种水基质中检测限与总有机碳（TOC）之间的正相关表明有机污染物对方法灵敏度有负面影响。环境样品中目标雌激素化合物的总量在17至9462 ng/L之间。
