Determination of estrogens and estrogen mimics by solid-phase extraction with liquid chromatography-tandem mass spectrometry

Yejin Li; Linyan Yang; Huajun Zhen; Xueming Chen; Mei Sheng; Kai Li; Weibo Xue; Huihui Zhao; Shujuan Meng; Guomin Cao

doi:10.1016/j.jchromb.2021.122559

Determination of estrogens and estrogen mimics by solid-phase extraction with liquid chromatography-tandem mass spectrometry

J Chromatogr B Analyt Technol Biomed Life Sci. 2021 Apr 1:1168:122559. doi: 10.1016/j.jchromb.2021.122559. Epub 2021 Jan 20.

Authors

Yejin Li¹, Linyan Yang², Huajun Zhen¹, Xueming Chen³, Mei Sheng¹, Kai Li¹, Weibo Xue¹, Huihui Zhao¹, Shujuan Meng⁴, Guomin Cao⁵

Affiliations

¹ School of Resources and Environmental Engineering, East China University of Science and Technology, Shanghai 200237, China.
² 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. Electronic address: lyyang@ecust.edu.cn.
³ Fujian Provincial Engineering Research Center of Rural Waste Recycling Technology, College of Environment and Resources, Fuzhou University, Fuzhou, Fujian 350116, China.
⁴ School of Space and Environment, Beihang University, Beijing 100191, China.
⁵ 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.

PMID: 33652260
DOI: 10.1016/j.jchromb.2021.122559

Abstract

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 (R² > 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.

Keywords: Estrogens; Liquid chromatography tandem mass spectrometry; Matrix effect; Solid phase extraction.

MeSH terms

Chromatography, Liquid / methods*
Estrogens / analysis*
Estrogens / chemistry
Estrogens / isolation & purification
Limit of Detection
Linear Models
Reproducibility of Results
Solid Phase Extraction / methods*
Tandem Mass Spectrometry / methods*
Water Pollutants, Chemical / analysis
Water Pollutants, Chemical / chemistry
Water Pollutants, Chemical / isolation & purification

Substances

Estrogens
Water Pollutants, Chemical