Journal of Chromatography A, 1022 (2004) 179–189 Simultaneous determination of endocrine disrupting phenolic compounds and steroids in water by solid-phase extraction–gas chromatography–mass spectrometry R. Liu, J.L. Zhou ∗ , A. Wilding Department of Biology and Environmental Science, School of Life Sciences, University of Sussex, Falmer, Brighton BN1 9QJ, UK Received 1 April 2003; received in revised form 15 September 2003; accepted 19 September 2003 Abstract A solid-phase extraction (SPE)–gas chromatography (GC)–mass spectrometry (MS) analytical method for the simultaneous separation and determination of endocrine disrupting chemicals (EDCs) from water samples is described in detail. Important and contrasting EDCs including estrone, 17-estradiol, 17-ethynylestradiol, 16-hydroxyestrone, 4-nonylphenol, bisphenol A and 4-tert-octylphenol were selected as the target compounds. The SPE technique, followed by the derivatisation with bis (trimethylsilyl) trifluoroacetamide was used for the extraction recoveries of target compounds from water samples. A number of parameters that may affect the recovery of EDCs, such as the type of SPE cartridges, eluents, as well as water properties including pH value, and concentration of salts and humic substances were investigated. It is shown that the Oasis cartridges produced the best recoveries of target EDCs while ethyl acetate was efficient in eluting EDCs from SPE cartridges. The recovery of some EDCs was enhanced by the addition of salt, but reduced by the increase in pH value and humic acid concentration. The optimised method was further verified by performing spiking experiments in natural river water and seawater matrices, with good recovery and reproducibility for all the selected compounds. The established method was successfully applied to environmental water samples from East and West Sussex, UK, for the determination of the target EDCs. © 2003 Elsevier B.V. All rights reserved. Keywords: Water analysis; Endocrine disruptors; Steroids; Phenolic compounds 1. Introduction Recently, a wide variety of chemicals that have been iden- tified to disrupt endocrine system of higher life forms, such as fish, wildlife and even humans, have attracted consider- able attentions worldwide. The so-called endocrine disrupt- ing chemicals (EDCs) fall into two main categories: those that occur naturally and those that are man-made. Among these compounds, naturally produced estrogens, such as 17-estradiol and estrone are mainly derived from excreta of humans and livestock, and 16-hydroxyestrone is the hep- atic metabolite of the natural estrone by 16-hydroxylation pathway. It has been shown that woman can excrete 7 g of estrone and 2.4 g of 17-estradiol per day [1]. The syn- ∗ Corresponding author. Tel.: +44-1273-877318; fax: +44-1273-677196. E-mail address: j.zhou@sussex.ac.uk (J.L. Zhou). thetic female hormone 17-ethynylestradiol has been used as an oral contraceptive pill. Apart from these steroids, the endocrine disrupting phenolic compounds, e.g. bisphenol A, 4-nonylphenol and 4-tert-octylphenol have been widely used in household and industrial processes (textile, paper, metal working fluids, detergents and polymeric material production). The EDCs may be released directly or indi- rectly to the aquatic environment, leading to the alternations of normal hormone function and physiological status in wildlife and humans, e.g. the development of testicular and prostate cancer and decreased sperm reproduction in humans, and feminisation and hermaphroditism in wildlife [2–5]. Generally, the analysis of EDCs has been accomplished by electrochemical method [6–9] and chromatographic techniques, such as high-performance liquid chromatogra- phy (HPLC) equipped with ultraviolet [10,11], fluorescence [12–15], electrochemical [16], or mass spectrometry (MS) 0021-9673/$ – see front matter © 2003 Elsevier B.V. All rights reserved. doi:10.1016/j.chroma.2003.09.035