On-line solid-phase extraction and fluorescence detection of selected endocrine disrupting chemicals in water by high-performance liquid chromatography

A high-performance liquid chromatographic method was developed to analyse selected endocrine disrupting chemicals in water by using automated on-line solid-phase extraction with a fluorescence detector. The excitation and emission wavelengths of the fluorescence detector were 230 nm and 290 nm, respectively. The selected endocrine disrupting chemicals include hormone steroids such as estradiol (E2), estriol (E3), ethynylestradiol (EE2), and ethynylestradiol 3-methyl ether (MeEE2) as well as nonylphenols (NP), octylphenols (OP), POE(1-2) nonyl phenol (NPE) and bisphenol A (BP). Three types of on-line cartridges (C18, PLRP-s and PRP-1) were tested to pre-concentrate the endocrine disruptors in deionised water. It was found that the recoveries of these chemicals at 1 microg/L were close to 100% except for 4-octyl phenol and 4-n-nonyl phenol, which had recoveries of about 40% to 80%. The two polymer cartridges (PLRP-s and PRP-1) gave higher recoveries than the C18 cartridges. The addition of methanol at 5% to 10% in water significantly improved the recovery of 4-octyl phenol and 4-n-nonyl phenol. The addition of methanol also led to an improvement in the recovery with C18 cartridges. With the addition of methanol in water samples, these three types of cartridges gave similar recoveries for the chemicals. The detection limits of this method ranged from 20 ng/L to 50 ng/L. A river water sample spiked with these chemicals was analysed using the above method and we found no interference with the peaks of the selected endocrine disrupting chemicals. The recoveries for these chemicals were more than 92% except for 4-NP with a recovery of 61%. This relatively simple method is useful for laboratory studies on the environmental fate of these endocrine disrupting chemicals in water.