Simultaneous determination of progestogens, androgens, estrogens and phenols in water, sediment and biological samples by enolisation–silylation with ASE-GPC-SPE-GC/MS

Abstract

This research has developed an enolisation–silylation with accelerated solvent extraction (ASE)-automated gel permeation chromatography (GPC)-solid phase extraction (SPE)-gas chromatography/mass spectrometry (GC/MS) analytical method for the simultaneous determination of twelve steroidal and phenolic endocrine disrupting chemicals (EDCs) in water, sediment and biological samples. The parameters of ASE have been optimized as follows: ethyl acetate as the extraction solvent, a static extraction time of 5 min, and 3 extraction cycles at 80 °C and 60 °C for sediment and biological samples, respectively. Clean-up of extracts was carried out by GPC with Sep-Pak C18 cartridges. The target compounds were eluted in the fraction from 7–14 min retention time, and then the extracts were obtained by solid phase extraction with Sep-Pak C18 cartridges after elution with 15 mL ethyl acetate. The final sample extracts were derivatized using N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA)/trimethyliodosilane (TMIS)/dithioerythreitol (DTE) (1000 : 2 : 5; v/v/w) as a derivatization reagent. Quantification was performed by gas chromatography-mass spectrometry (GC-MS) with electron ionisation (EI) and selected ion monitoring (SIM) mode. The method was validated by spiking experiments which showed low method detection limits, good recovery (60.28% to 95.46%) and reproducibility (RSD < 10%). The proposed methods were successfully applied to the determination of the target EDCs in environmental samples taken from the Laoyu River and a local market in Yunnan, China. This method had better practicability and feasibility for simultaneous determination of progestogens, androgens, estrogens and phenols in water, sediment and biological samples. This technique is more fast, simple and precise than some other methods, and has a wide range of applications. It is beneficial to study the occurrence, fate and bioaccumulation of these compounds in the environment.