Skip to main content
SpringerLink
Log in

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

  • Research Paper
  • Published:
Analytical and Bioanalytical Chemistry Aims and scope Submit manuscript

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.

ᅟ

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4

Similar content being viewed by others

References

  1. Kozlowska-Tylingo K, Namieśnik J, Górecki T. Determination of estrogenic endocrine disruptors in environmental samples—a review of chromatographic methods. Crit Rev Anal Chem. 2010;40:194–201. https://doi.org/10.1080/10408347.2010.490488.

    Article  CAS  Google Scholar 

  2. Chen HC, Kuo HW, Ding WH. Determination of estrogenic compounds in wastewater using liquid chromatography-tandem mass spectrometry with electrospray and atmospheric pressure photoionization following desalting extraction. Chemosphere. 2009;74:508–14. https://doi.org/10.1016/j.chemosphere.2008.09.089.

    Article  CAS  PubMed  Google Scholar 

  3. Liu ZH, Lu GN, Yin H, Dang Z, Littier H, Liu Y. Sample-preparation methods for direct and indirect analysis of natural estrogens. TrAC - Trends Anal Chem. 2015;64:149–64. https://doi.org/10.1016/j.trac.2014.09.003.

    Article  CAS  Google Scholar 

  4. Reddy S, Iden CR, Brownawell BJ. Analysis of steroid conjugates in sewage influent and effluent by liquid chromatography-tandem mass spectrometry. Anal Chem. 2005;77:7032–8. https://doi.org/10.1021/ac050699x.

    Article  CAS  PubMed  Google Scholar 

  5. Kuster M. José López De Alda M, Barceló D. Analysis and distribution of estrogens and progestogens in sewage sludge, soils and sediments. TrAC - Trends Anal Chem. 2004;23:790–8. https://doi.org/10.1016/j.trac.2004.08.007.

    Article  CAS  Google Scholar 

  6. Corrotea Y, Aguilera N, Honda L, Richter P. Determination of hormones in wastewater using rotating disk sorptive extraction and gas chromatography – mass spectrometry. Anal Lett. 2015;2719:1344–58. https://doi.org/10.1080/00032719.2015.1098653.

    Article  CAS  Google Scholar 

  7. Fang TY, Praveena SM. deBurbure C, Aris AZ, Ismail SNS, Rasdi I. Analytical techniques for steroid estrogens in water samples - a review. Chemosphere. 2016;165:358–68. https://doi.org/10.1016/j.chemosphere.2016.09.051.

    Article  CAS  PubMed  Google Scholar 

  8. Huang B, Wang B, Ren D, Jin W, Liu J, Peng J, et al. Occurrence, removal and bioaccumulation of steroid estrogens in Dianchi Lake catchment. China. Environ Int. 2013;59:262–73. https://doi.org/10.1016/j.envint.2013.06.018.

    Article  CAS  PubMed  Google Scholar 

  9. Beck I-C, Bruhn R, Gandrass J, Ruck W. Liquid chromatography–tandem mass spectrometry analysis of estrogenic compounds in coastal surface water of the Baltic Sea. J Chromatogr A. 2005;1090:98–106. https://doi.org/10.1016/j.chroma.2005.07.013.

    Article  CAS  PubMed  Google Scholar 

  10. Gao G, Li S, Li S, Wang Y, Zhao P, Zhang X, et al. A combination of computational−experimental study on metal-organic frameworks MIL-53(Al) as sorbent for simultaneous determination of estrogens and glucocorticoids in water and urine samples by dispersive micro-solid-phase extraction coupled to UPLC-MS/MS. Talanta. 2018;180:358–67. https://doi.org/10.1016/j.talanta.2017.12.071.

    Article  CAS  PubMed  Google Scholar 

  11. Wang HX, Zhou Y, Jiang QW. Simultaneous screening of estrogens, progestogens, and phenols and their metabolites in potable water and river water by ultra-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry. Microchem J. 2012;100:83–94. https://doi.org/10.1016/j.microc.2011.09.010.

    Article  CAS  Google Scholar 

  12. Liu S, Ying G-G, Zhao J-L, Chen F, Yang B, Zhou L-J, et al. Trace analysis of 28 steroids in surface water, wastewater and sludge samples by rapid resolution liquid chromatography-electrospray ionization tandem mass spectrometry. J Chromatogr A. 2011;1218:1367–78. https://doi.org/10.1016/j.chroma.2011.01.014.

    Article  CAS  PubMed  Google Scholar 

  13. Lien G-W, Chen C-Y, Wang G-S. Comparison of electrospray ionization, atmospheric pressure chemical ionization and atmospheric pressure photoionization for determining estrogenic chemicals in water by liquid chromatography tandem mass spectrometry with chemical derivatizations. J Chromatogr A. 2009;1216:956–66. https://doi.org/10.1016/j.chroma.2008.12.023.

    Article  CAS  PubMed  Google Scholar 

  14. Shareef A, Angove MJ, Wells JD. Optimization of silylation using N-methyl-N-(trimethylsilyl)-trifluoroacetamide, N,O-bis-(trimethylsilyl)-trifluoroacetamide and N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide for the determination of the estrogens estrone and 17α-ethinylestradi. J Chromatogr A. 2006;1108:121–8. https://doi.org/10.1016/j.chroma.2005.12.098.

    Article  CAS  PubMed  Google Scholar 

  15. López De Alda MJ, Barceló D. Determination of steroid sex hormones and related synthetic compounds considered as endocrine disrupters in water by liquid chromatography-diode array detection-mass spectrometry. J Chromatogr A. 2000;892:391–406. https://doi.org/10.1016/S0021-9673(00)00068-6.

    Article  PubMed  Google Scholar 

  16. Labadie P, Hill EM. Analysis of estrogens in river sediments by liquid chromatography-electrospray ionisation mass spectrometry. Comparison of tandem mass spectrometry and time-of-flight mass spectrometry. J Chromatogr A. 2007;1141:174–81. https://doi.org/10.1016/j.chroma.2006.12.045.

    Article  CAS  PubMed  Google Scholar 

  17. Yan W, Zhao L, Feng Q, Wei Y, Lin J-M. Simultaneous determination of ten estrogens and their metabolites in waters by improved two-step SPE followed by LC–MS. Chromatographia. 2009;69:621–8. https://doi.org/10.1365/s10337-009-0957-7.

    Article  CAS  Google Scholar 

  18. Qin F, Zhao YY, Sawyer MB, Li X-F. Column-switching reversed phase-hydrophilic interaction liquid chromatography/tandem mass spectrometry method for determination of free estrogens and their conjugates in river water. Anal Chim Acta. 2008;627:91–8. https://doi.org/10.1016/j.aca.2008.07.036.

    Article  CAS  PubMed  Google Scholar 

  19. Salvador A, Moretton C, Piram A, Faure R. On-line solid-phase extraction with on-support derivatization for high-sensitivity liquid chromatography tandem mass spectrometry of estrogens in influent/effluent of wastewater treatment plants. J Chromatogr A. 2007;1145:102–9. https://doi.org/10.1016/j.chroma.2007.01.055.

    Article  CAS  PubMed  Google Scholar 

  20. Li X, Franke AA. Improved profiling of estrogen metabolites by orbitrap LC/MS. Steroids. 2014;99:84–90. https://doi.org/10.1016/j.steroids.2014.12.005.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  21. Khedr A, Alahdal AM. Liquid chromatography–tandem mass spectrometric analysis of ten estrogen metabolites at sub-picogram levels in breast cancer women. J Chromatogr B Anal Technol Biomed Life Sci. 2016;1031:181–8. https://doi.org/10.1016/j.jchromb.2016.07.051.

    Article  CAS  Google Scholar 

  22. Farlow DW, Xu X, Veenstra TD. Quantitative measurement of endogenous estrogen metabolites, risk-factors for development of breast cancer, in commercial milk products by LC-MS/MS. J Chromatogr B Anal Technol Biomed Life Sci. 2009;877:1327–34. https://doi.org/10.1016/j.jchromb.2009.01.032.

    Article  CAS  Google Scholar 

  23. Xu X, Veenstra TD, Fox SD, Roman JM, Issaq HJ, Falk R, et al. Measuring fifteen endogenous estrogens simultaneously in human urine by high-performance liquid chromatography-mass spectrometry. Anal Chem. 2005;77:6646–54. https://doi.org/10.1021/ac050697c.

    Article  CAS  PubMed  Google Scholar 

  24. Xu X, Keefer LK, Ziegler RG, Veenstra TD. A liquid chromatography-mass spectrometry method for the quantitative analysis of urinary endogenous estrogen metabolites. Nat Protoc. 2007;2:1350–5. https://doi.org/10.1038/nprot.2007.176.

    Article  CAS  PubMed  Google Scholar 

  25. Tomšíková H, Aufartová J, Solich P, Nováková L, Sosa-Ferrera Z, Santana-Rodríguez JJ. High-sensitivity analysis of female-steroid hormones in environmental samples. TrAC - Trends Anal Chem. 2012;34:35–57. https://doi.org/10.1016/j.trac.2011.11.008.

    Article  CAS  Google Scholar 

  26. Huang J, Sun J, Chen Y, Song Y, Dong L, Zhan Q, et al. Analysis of multiplex endogenous estrogen metabolites in human urine using ultra-fast liquid chromatography-tandem mass spectrometry: a case study for breast cancer. Anal Chim Acta. 2012;711:60–8. https://doi.org/10.1016/j.aca.2011.10.058.

    Article  CAS  PubMed  Google Scholar 

  27. Bussy U, Chung-Davidson YW, Buchinger TJ, Li K, Li W. High-sensitivity determination of estrogens in fish plasma using chemical derivatization upstream UHPLC–MSMS. Steroids. 2017;123:13–9. https://doi.org/10.1016/j.steroids.2017.04.003.

    Article  CAS  PubMed  Google Scholar 

  28. Ferreira MS, Arruda AMM, Pepi GT, Martho AC, Maximiano PM, Ricci LSOBO, et al. High sensitivity method validated to quantify estradiol in human plasma by LC–MS/MS. J Chromatogr B Anal Technol Biomed Life Sci. 2017;1064:109–14. https://doi.org/10.1016/j.jchromb.2017.09.005.

    Article  CAS  Google Scholar 

  29. Huang HJ, Chiang PH, Chen SH. Quantitative analysis of estrogens and estrogen metabolites in endogenous MCF-7 breast cancer cells by liquid chromatography-tandem mass spectrometry. J Chromatogr B Anal Technol Biomed Life Sci. 2011;879:1748–56. https://doi.org/10.1016/j.jchromb.2011.04.020.

    Article  CAS  Google Scholar 

  30. Benijts T, Dams R, Günther W, Lambert W, De Leenheer A. Analysis of estrogenic contaminants in river water using liquid chromatography coupled to ion trap based mass spectrometry. Rapid Commun Mass Spectrom. 2002;16:1358–64. https://doi.org/10.1002/rcm.716.

    Article  CAS  PubMed  Google Scholar 

  31. Anari MR, Bakhtiar R, Zhu B, Huskey S, Franklin RB, Evans DC. Derivatization of ethinylestradiol with dansyl chloride to enhance electrospray ionization: application in trace analysis of ethinylestradiol in rhesus monkey plasma. Anal Chem. 2002;74:4136–44. https://doi.org/10.1021/ac025712h.

    Article  CAS  PubMed  Google Scholar 

  32. Tan X, Li Z, Deng L, Zhao S, Wang M. Analysis of 13 kinds of steroid hormones in raw milk using modified QuEChERS method combined with UPLC-QTOF-MS. J Integr Agric. 2016;15:2163–74. https://doi.org/10.1016/S2095-3119(16)61386-2.

    Article  CAS  Google Scholar 

  33. Fuentes E, Báez ME, Díaz J. Microwave-assisted extraction at atmospheric pressure coupled to different clean-up methods for the determination of organophosphorus pesticides in olive and avocado oil. J Chromatogr A. 2009;1216:8859–66. https://doi.org/10.1016/j.chroma.2009.10.082.

    Article  CAS  PubMed  Google Scholar 

Download references

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).

Author information

Authors and Affiliations

  1. Department of Inorganic and Analytical Chemistry, Faculty of Chemical and Pharmaceutical Sciences, University of Chile, P.O. Box 233, Santiago, Chile

    Luis Honda & Pablo Richter

  2. Department of Chemistry, Faculty of Sciences, University of Chile, P.O. Box 653, Santiago, Chile

    Mercedes Becerra-Herrera

Authors
  1. Luis Honda
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Mercedes Becerra-Herrera
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Pablo Richter
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Pablo Richter.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Electronic supplementary material

ESM 1

(PDF 213 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Honda, L., Becerra-Herrera, M. & Richter, P. 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. Anal Bioanal Chem 410, 7909–7919 (2018). https://doi.org/10.1007/s00216-018-1412-0

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00216-018-1412-0

Keywords

Search

Navigation