Simultaneous measurement of free and conjugated estrogens in surface water using capillary liquid chromatography tandem mass spectrometry

Abstract

Given detrimental impacts induced by estrogens at trace level, determination of them is significant but challenging due to their low content in environmental samples and inherent weak ionisation. A modified derivatisation-based methodology was applied for the first time to detect estrogen in free and conjugated forms including some isomers simultaneously using liquid chromatography tandem mass spectrometry (LC-MSn). Derivatisation reaction with previously used 1,2-dimethyl-1H-imidazole-5-sulphonyl chloride allowed significant increase of mass spectrometric signal of analytes and also provided distinctive fragmentation for their confirmation even in complicated matrix. Then satisfactory recovery (>75%) for the majority of analytes was achieved following optimisation of solid phase extraction (SPE) factors. The linearity was validated over a wide concentration with the correlation coefficient around 0.995. The repeatability of this methodology was also confirmed via the intra-day and inter-day precision and was less than 11.73%. Validation of method quantification limits (MQLs) for all chosen estrogens was conducted using 1000 mL surface water, ranging from 7.0 to 132.3 pg L-1. The established methodology was applied to profile presence of targeted estrogens in natural surface water samples. Out of the ten compounds of interest, three free estrogens (E1, E2, E3) and two sulphate estrogens (E1-3S and E2-3S) were found over their MQLs, being in the range of 0.05-0.32 ng L-1.