Determination of estrogens by solid-phase quadruplex stable isotope dansylation coupled with liquid chromatography-high resolution mass spectrometry in environmental samples.

Estrogens distribute widely in the environment as endocrine-disrupting chemicals (EDCs), which have to be monitored to evaluate their environmental impact. Aim to improve the analytical throughput of liquid chromatography-high resolution mass spectrometry (LC-HRMS), a quadruplex stable isotope dansylation method was developed, with which three real samples could be quantitatively analyzed in one injection. As the estrogens were at trace level in complex matrices, magnetic solid-phase extraction (MSPE) was applied to enrich these analytes and remove the interfaces. By integrating MSPE and quadruplex stable isotope dansylation, a solid-phase quadruplex labeling method was developed for the LC-HRMS analysis of estrogen analogues. For the tested seven estrogens, the developed method showed low detection limits (0.1-0.5 ng/L for pond water and 0.01-0.05 μg/kg for poultry manure), good precision (RSD < 5.5%) and accuracy (96.8-108.3%). The method was applied in the determination of estrogens in environmental samples, and the results revealed that all the tested estrogens were present in the estuary water (unquantifiable to 71.2 ng/L) and chicken manure (undetectable to 25.43 μg/kg).