Optimisation of derivatisation for the analysis of estrogenic compounds in water by solid-phase extraction gas chromatography–mass spectrometry

An optimisation of derivatisation methods for the simultaneous determination of endocrine disrupting chemicals (EDCs) in water by solid-phase extraction (SPE) gas chromatography–mass spectrometry (GC–MS) was developed in this study. Seven highly potent EDCs including 17ß-estradiol (E2), estrone (E1), 16a-hydroxyestrone, 17a-ethynylestradiol (EE2), bisphenol A, 4-nonylphenol and 4-tert-octylphenol were selected as the target compounds. The SPE technique, followed by the derivatisation with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) was used for the extraction recoveries of compounds from water and effluent samples. The stability of the silylation derivatives under different reaction conditions was investigated. The combined use of BSTFA and pyridine as derivatisation reagents, together with the use of hexane as the final solvent, was preferred in order to generate more stable derivatives of EDCs. The relative response factor (RRF) of all derivatives except that of EE2 was stable 120 h after derivatisation. The addition of pyridine as derivatisation reagent with BSTFA can prevent the conversion of EE2 to other products during the reaction. Several parameters that may affect the recovery of EDCs, such as the SPE flow rate, and water properties including aquatic colloid content and surfactant concentration were tested. The results showed that the flow rate (1–25 mL min-1), colloid concentration (0–50 mg L-1) and surfactants concentration (0–10 µg L-1) did not cause significant decrease in the EDCs recovery.