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Simultaneous speciation analysis of Hg and Se in fish by high-performance liquid chromatography and inductively coupled plasma-mass spectrometry following microwave-assisted enzymatic hydrolysis

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Abstract

This study reports the development and validation of a new analytical method for simultaneous speciation analysis of Se and Hg in fish muscle. For this purpose, four Se species (selenite/Se(IV), selenate/Se(VI), selenomethionine/SeMet, and selenocysteine/SeCys) and two Hg species (inorganic mercury/iHg and methylmercury/MeHg) were extracted simultaneously by microwave-assisted enzymatic hydrolysis and then separated by HPLC in less than 15 min by using a column with both anion and cation exchange mechanisms and a mobile phase consisting of a mixture of methanol 5% (v/v), 45 mM HNO3, 0.015% 2-mercaptoethanol, and 1.5 mM sodium 3-mercapto-1-propanesulfonate. The separated species of Hg and Se were detected online by inductively coupled plasma-mass spectrometry (ICP-MS). The speciation analysis method was validated by means of the accuracy profile approach by carrying out three series of measurements in duplicate on three different days over a time-span of 3 weeks. The limits of quantification (LOQ) are in the range of 0.010–0.013 mg/kg wet weight (ww) for all selenium species, except for Se(IV) (0.15 mg/kg ww), while the coefficient of variation in terms of intermediate reproducibility (CVR) was < 7%. The LOQ for MeHg was 0.006 mg/kg ww, while the CVR was 3%. The method was successfully applied to the analysis of muscle samples from four different fish species: rainbow trout, tuna, swordfish, and dogfish.

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Acknowledgements

This study is a contribution to the Ph.D. research project (MERSEL-FISH) and it was jointly funded by ANSES (France) and INSA (Portugal).

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Authors and Affiliations

  1. Laboratory for Food Safety, ANSES, Univ Paris Est Creteil, 14 Rue Pierre Et Marie Curie, 94700, Maisons-Alfort, France

    M. Ribeiro, E. Galli, A. Leufroy & P. Jitaru

  2. Departamento de Alimentação E Nutrição, Instituto Nacional de Saúde Doutor Ricardo Jorge, INSA IP, Avenida Padre Cruz, 1649-016, Lisbon, Portugal

    M. Ribeiro & I. Castanheira

  3. Centro de Química Estrutural, Institute of Molecular Sciences, Departamento de Engenharia Química, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001, Lisbon, Portugal

    M. Ribeiro & J. A. L. Silva

  4. Strategy and Programmes Department, ANSES, 94701, Maisons-Alfort, France

    T. Guérin

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  1. M. Ribeiro
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Contributions

Conceptualisation: Mariana Ribeiro, José Armando Luísa da Silva, Isabel Castanheira, Axelle Leufroy, and Petru Jitaru. Data curation: Mariana Ribeiro, Isabel Castanheira, Axelle Leufroy, and Petru Jitaru. Formal analysis: Mariana Ribeiro and Eleonora Galli. Funding acquisition: Isabel Castanheira, Axelle Leufroy, and Petru Jitaru. Investigation: Mariana Ribeiro, Isabel Castanheira, and Petru Jitaru. Methodology: Mariana Ribeiro, Eleonora Galli, José Armando Luísa da Silva, Isabel Castanheira, Axelle Leufroy, and Petru Jitaru. Project administration: Isabel Castanheira and Petru Jitaru. Resources: Thierry Guérin, Isabel Castanheira, and Petru Jitaru. Supervision: Isabel Castanheira, Axelle Leufroy, and Petru Jitaru. Validation: Mariana Ribeiro, Eleonora Galli, José Armando Luísa da Silva, Isabel Castanheira, Axelle Leufroy, and Petru Jitaru. Roles/writing—original: Mariana Ribeiro. Writing—review and editing: Thierry Guérin, Isabel Castanheira, Axelle Leufroy, and Petru Jitaru.

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Correspondence to P. Jitaru.

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Ribeiro, M., Galli, E., Guérin, T. et al. Simultaneous speciation analysis of Hg and Se in fish by high-performance liquid chromatography and inductively coupled plasma-mass spectrometry following microwave-assisted enzymatic hydrolysis. Anal Bioanal Chem 415, 7175–7186 (2023). https://doi.org/10.1007/s00216-023-04984-1

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