Optimisation of an in-tube solid phase microextraction method coupled with HPLC for determination of some oestrogens in environmental liquid samples using different capillary columns

Abstract

A simple on-line method for simultaneous determination of some oestrogens including oestriol (E3), norethisterone (NORE), ethynylestradiol (EE2), D-norgestrel (NORG) and bisphenol A (BPA), in environmental liquid samples was developed by coupling in-tube solid phase microextraction (in-tube SPME) to high-performance liquid chromatography with diode array (DAD) and fluorescence (FLD) detectors. Two capillary chromatographic columns (Supel-Q™ and Carboxen™ 1006 porous layer open tubular) were selected to develop this method. To achieve optimum extraction performance, several parameters were investigated including number of draw/eject cycles and the sample volume for each of the columns. Reproducibility was satisfactory for inter- and intra-day precision, yielding % RSDs of less than 10% and 7.6%, respectively. Limits of detection (LODs) and quantification (LOQs) for the proposed method using a DAD detector were achieved in the ranges of 0.04–0.63 ng mL⁻¹ and 0.12–1.9 ng mL⁻¹, depending of the capillary column used. Fluorescence detection improved these parameters for E3, BPA and EE2, obtaining LODs of 0.005–0.03 ng mL⁻¹ and LOQs of 0.015–0.08 ng mL⁻¹ using Supel-Q and LODs of 0.01–0.015 ng mL⁻¹ and LOQs of 0.025–0.04 ng mL⁻¹ using Carboxen. The proposed method was successfully applied to spiked environmental waters obtaining recoveries greater than 80%.

Keywords:

• oestrogens
• endocrine disruptor chemicals (EDCs)
• in-tube SPME
• sea water
• effluent of wastewater treatment plant
• liquid chromatography

Acknowledgements

This work was supported by funds provided by the Spanish Ministry of Science and Innovation (MICINN), Research Project no. CTQ 2010-20554. Jana Aufartová acknowledges the financial support of the Grant Agency of the Academy of Sciences of the Czech Republic (KJB 601100901). SVV/2011/263002.