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Liquid chromatography–time-of-flight high-resolution mass spectrometry study and determination of the dansylated products of estrogens and their hydroxylated metabolites in water and wastewater

  • Luis Honda
  • Mercedes Becerra-Herrera
  • Pablo Richter
Research Paper

Abstract

A method combining liquid chromatography with a dual-probe ultraspray electrospray ionization (ESI) source and time-of-flight high-resolution mass spectrometry (LC-ESI-TOF/MS) was developed for the simultaneous determination of four steroidal sex hormones, estrone (E1), 17β-estradiol (E2), 17α-ethinyl estradiol (EE2), and estriol (E3), as well as five of their hydroxylated metabolites, 2-hydroxyestrone (2-OHE1), 4-hydroxyestrone (4-OHE1), 16α-hydroxyestrone (16-OHE1), 2-hydroxyestradiol (2-OHE2), and 4-hydroxyestradiol (4-OHE2), in water samples in a short chromatographic run of 10 min. Derivatization of the analytes was optimized using dansyl chloride as the derivatizing agent. Under optimal positive ionization conditions, the following signals, which had not been previously reported, were observed (with theoretical values of m/z 377.1373 for 2- and 4-OHE1 and 378.1452 for 2- and 4-OHE2), corresponding to doubly derivatized catechol estrogens in the form of [M+2H]2+. These mass spectrometric signals were more abundant than those reported previously for the [M+H]+ forms of these hydroxylated metabolites. Solid-phase extraction (SPE) with an octadecyl-endcapped sorbent was used to pretreat tap water and effluent from a wastewater treatment plant (WWTP) in Santiago, Chile. The method achieved the simple, fast, and sensitive measurement of nine estrogens with quantitative recoveries (higher than 85.4%). Detection and quantification limits were between 1 and 17 ng L–1 and between 3 and 58 ng L–1, respectively, for all compounds in water. The estrogens E1 and E2 were found in WWTP effluent at concentrations of 7 ± 1 and 41 ± 1 ng L–1, respectively, and EE2 was detected at a concentration below the limit of quantitation. This study shows that the proposed method is suitable for the accurate, rapid, and selective determination of all these analytes at trace levels.

Graphical abstract

Keywords

LC-ESI-TOF/MS Estrogenic hormones Catechol estrogens Positive electrospray ionization Derivatization reaction Wastewater 

Notes

Acknowledgements

The authors would like to thank FONDECYT (Regular Grant 1180742) and FONDEQUIP (Project EQM130119) for financial support. LH would like to thank CONICYT for his doctoral fellowship (21140560) and MBH thank to CONICYT (PAI79170018).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

216_2018_1412_MOESM1_ESM.pdf (213 kb)
ESM 1 (PDF 213 kb)

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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Luis Honda
    • 1
  • Mercedes Becerra-Herrera
    • 2
  • Pablo Richter
    • 1
  1. 1.Department of Inorganic and Analytical Chemistry, Faculty of Chemical and Pharmaceutical SciencesUniversity of ChileSantiagoChile
  2. 2.Department of Chemistry, Faculty of SciencesUniversity of ChileSantiagoChile

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