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Validation of an isotope dilution mass spectrometry (IDMS) measurement procedure for the reliable quantification of steroid hormones in waters

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Abstract

Reliable data are compulsory to efficiently monitor pollutants in aquatic environments, particularly steroid hormones that can exert harmful effects at challenging analytical levels below the ng L−1. An isotope dilution two-step solid-phase extraction followed by an ultra-performance liquid chromatography separation coupled to tandem mass spectrometry (UPLC-MS/MS) detection method was validated for the quantification of 21 steroid hormones (androgens, estrogens, glucocorticoids, and progestogens) in whole waters. To achieve a realistic and robust assessment of the performances of this method, the validation procedure was conducted using several water samples representative of its intended application. These samples were characterized in terms of concentration of ionic constituents, suspended particulate matter (SPM), and dissolved organic carbon contents (DOC). For estrogens that are part of the European Water Framework Directive Watchlist (17beta-estradiol and estrone), the performances met the European requirements (decision 2015/495/EU) in terms of limit of quantification (LQ) and measurement uncertainty. For 17alpha-ethinylestradiol, the challenging LQ of 0.035 ng L−1 was reached. More generally, for 15 compounds out of 21, the accuracy, evaluated in intermediate precision conditions at concentrations ranging between 0.1 and 10 ng L−1, was found to be within a 35% tolerance. The evaluation of the measurement uncertainty was realized following the Guide to the expression of Uncertainty in Measurement. Finally, a water monitoring survey demonstrated the suitability of the method and pointed out the contamination of Belgium rivers by five estrogens (17alpha-ethinylestradiol, estriol, 17alpha-estradiol, 17beta-estradiol, and estrone) and three glucocorticoids (betamethasone, cortisol, and cortisone) which have been up to now poorly documented in European rivers.

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The datasets generated during and/or analyzed during the current study are available from the corresponding author on reasonable request.

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Acknowledgements

The authors would like to thank Dr. Nathalie Guigues from LNE for her support during the writing of the present paper.

Funding

The ANRT (Association Nationale de la Recherche et de la Technologie) (2017/1131) funded Elodie Mirmont’ PhD work.

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Authors and Affiliations

  1. Laboratoire National de métrologie et d’Essai (LNE), 1 rue Gaston Boissier, 75015, Paris, France

    Elodie Mirmont, Amandine Bœuf, Mélissa Charmel & Béatrice Lalère

  2. Nancy Laboratory for Hydrology, Water Chemistry Unit, ANSES, 40 rue Lionnois, 54 000, Nancy, France

    Sophie Lardy-Fontan

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  1. Elodie Mirmont
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  2. Amandine Bœuf
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Contributions

Conceptualization: Elodie Mirmont, Amandine Boeuf, Sophie Lardy-Fontan

Methodology: Elodie Mirmont, Amandine Boeuf, Sophie Lardy-Fontan

Investigation: Elodie Mirmont, Mélissa Charmel

Writing original draft: Elodie Mirmont, Amandine Boeuf, Sophie Lardy-Fontan

Writing review and editing: Elodie Mirmont, Amandine Boeuf, Mélissa Charmel, Béatrice Lalère, Sophie Lardy-Fontan

Visualization: Elodie Mirmont

Supervision: Amandine Boeuf, Sophie Lardy-Fontan

Project administration: Amandine Boeuf, Sophie Lardy-Fontan

Funding acquisition: Amandine Boeuf, Béatrice Lalère, Sophie Lardy-Fontan

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Correspondence to Amandine Bœuf.

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Mirmont, E., Bœuf, A., Charmel, M. et al. Validation of an isotope dilution mass spectrometry (IDMS) measurement procedure for the reliable quantification of steroid hormones in waters. Anal Bioanal Chem 415, 3215–3229 (2023). https://doi.org/10.1007/s00216-023-04698-4

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