Liquid chromatography–tandem mass spectrometry analysis of estrogenic compounds in coastal surface water of the Baltic Sea

An analytical method has been developed for the determination of five naturally occurring estrogens (estradiol, estriol, estrone, genistein, daidzein), one synthetic hormone (ethynylestradiol) and three xenoestrogens (4-nonylphenol (NP), 4-tert-octylphenol (4-tert-OP), bisphenol A (BPA)) in coastal marine waters. The procedure includes a solid-phase extraction of approx. fifty litres of water samples on the solid-phase copolymer Oasis HLB followed by a clean-up on silica. Twenty-five percent aliquots were used for the analytical determination of the analytes using high performance liquid chromatography coupled with electrospray-ionisation tandem mass spectrometry (HPLC–ESI-MS/MS). Calculated extraction recoveries between 52 (4-tert-octylphenol) and 91% (nonylphenol) were obtained for the method developed. Matrix interferences occurring during electrospray ionisation were quantified by spiking the extracts prior to the measurements. Method detection limits ranged from 0.02 (estrone) to 1 ng L−1 (estriol). The method was applied to determine environmental estrogens in coastal waters of the Baltic Sea. The analyses showed the presence of five compounds at levels between 0.10 (estrone) and 17 ng L−1 (ethynylestradiol).