Mercury Isotope Fractionation by Internal Demethylation and Biomineralization Reactions in Seabirds: Implications for Environmental Mercury Science
International audience A prerequisite for environmental and toxicological applications of mercury (Hg) stable isotopes in wildlife and humans is quantifying the isotopic fractionation of biological reactions. Here, we measured stable Hg isotope values of relevant tissues of giant petrels (Macronecte...
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Online Access: | https://hal.science/hal-03425602 https://hal.science/hal-03425602/document https://hal.science/hal-03425602/file/202Hg_Petrel_HAL.pdf https://doi.org/10.1021/acs.est.1c04388 |
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ftunivsavoie:oai:HAL:hal-03425602v1 2024-04-21T07:47:16+00:00 Mercury Isotope Fractionation by Internal Demethylation and Biomineralization Reactions in Seabirds: Implications for Environmental Mercury Science Manceau, Alain Brossier, Romain Janssen, Sarah, E Rosera, Tylor, J Krabbenhoft, David, P Cherel, Yves Bustamante, Paco Poulin, Brett, A Centre National de la Recherche Scientifique (CNRS) Institut des Sciences de la Terre (ISTerre) Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Université Savoie Mont Blanc (USMB Université de Savoie Université de Chambéry )-Centre National de la Recherche Scientifique (CNRS)-Université Gustave Eiffel-Université Grenoble Alpes (UGA) Upper Midwest Water Science Center U.S Geological Survey Centre d'Études Biologiques de Chizé - UMR 7372 (CEBC) La Rochelle Université (ULR)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE) LIttoral ENvironnement et Sociétés (LIENSs) La Rochelle Université (ULR)-Centre National de la Recherche Scientifique (CNRS) Department of Environmental Toxicology University of California (UC) 2021-10-19 https://hal.science/hal-03425602 https://hal.science/hal-03425602/document https://hal.science/hal-03425602/file/202Hg_Petrel_HAL.pdf https://doi.org/10.1021/acs.est.1c04388 en eng HAL CCSD American Chemical Society info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.est.1c04388 hal-03425602 https://hal.science/hal-03425602 https://hal.science/hal-03425602/document https://hal.science/hal-03425602/file/202Hg_Petrel_HAL.pdf doi:10.1021/acs.est.1c04388 info:eu-repo/semantics/OpenAccess ISSN: 0013-936X EISSN: 1520-5851 Environmental Science and Technology https://hal.science/hal-03425602 Environmental Science and Technology, 2021, 55 (20), pp.13942-13952. ⟨10.1021/acs.est.1c04388⟩ Mercury isotope fractionation toxicology bird [SDV]Life Sciences [q-bio] info:eu-repo/semantics/article Journal articles 2021 ftunivsavoie https://doi.org/10.1021/acs.est.1c04388 2024-04-11T00:37:57Z International audience A prerequisite for environmental and toxicological applications of mercury (Hg) stable isotopes in wildlife and humans is quantifying the isotopic fractionation of biological reactions. Here, we measured stable Hg isotope values of relevant tissues of giant petrels (Macronectes spp.). Isotopic data were interpreted with published HR-XANES spectroscopic data that document a step-wise transformation of methylmercury (MeHg) to Hg-tetraselenolate (Hg(Sec)4) and mercury selenide (HgSe) (Sec = selenocysteine). By mathematical inversion of isotopic and spectroscopic data, identical δ 202 Hg values for MeHg (2.69 ± 0.04 ‰), Hg(Sec)4 (−1.37 ± 0.06 ‰), and HgSe (0.18 ± 0.02 ‰) were determined in 23 tissues of eight birds from the Kerguelen Islands and Adélie Land (Antarctica). Isotopic differences in δ 202 Hg between MeHg and Hg(Sec)4 (−4.1 ± 0.1 ‰) reflect mass-dependent fractionation from a kinetic isotope effect due to the MeHg → Hg(Sec)4 demethylation reaction. Surprisingly, Hg(Sec)4 and HgSe differed isotopically in δ 202 Hg (+1.6 ± 0.1 ‰) and mass-independent anomalies (i.e., changes in Δ 199 Hg of ≤0.3 ‰), consistent with equilibrium isotope effects of massdependent and nuclear volume fractionation from Hg(Sec)4 → HgSe biomineralization. The invariance of species-specific δ 202 Hg values across tissues and individual birds reflects the kinetic lability of Hgligand bonds and tissue-specific redistribution of MeHg and inorganic Hg, likely as Hg(Sec)4. These observations provide fundamental information necessary to improve the interpretation of stable Hg isotope data and provoke a revisitation of processes governing isotopic fractionation in biota and toxicological risk assessment in wildlife. Article in Journal/Newspaper Antarc* Antarctica Giant Petrels Kerguelen Islands Université Savoie Mont Blanc: HAL Environmental Science & Technology 55 20 13942 13952 |
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Université Savoie Mont Blanc: HAL |
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English |
topic |
Mercury isotope fractionation toxicology bird [SDV]Life Sciences [q-bio] |
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Mercury isotope fractionation toxicology bird [SDV]Life Sciences [q-bio] Manceau, Alain Brossier, Romain Janssen, Sarah, E Rosera, Tylor, J Krabbenhoft, David, P Cherel, Yves Bustamante, Paco Poulin, Brett, A Mercury Isotope Fractionation by Internal Demethylation and Biomineralization Reactions in Seabirds: Implications for Environmental Mercury Science |
topic_facet |
Mercury isotope fractionation toxicology bird [SDV]Life Sciences [q-bio] |
description |
International audience A prerequisite for environmental and toxicological applications of mercury (Hg) stable isotopes in wildlife and humans is quantifying the isotopic fractionation of biological reactions. Here, we measured stable Hg isotope values of relevant tissues of giant petrels (Macronectes spp.). Isotopic data were interpreted with published HR-XANES spectroscopic data that document a step-wise transformation of methylmercury (MeHg) to Hg-tetraselenolate (Hg(Sec)4) and mercury selenide (HgSe) (Sec = selenocysteine). By mathematical inversion of isotopic and spectroscopic data, identical δ 202 Hg values for MeHg (2.69 ± 0.04 ‰), Hg(Sec)4 (−1.37 ± 0.06 ‰), and HgSe (0.18 ± 0.02 ‰) were determined in 23 tissues of eight birds from the Kerguelen Islands and Adélie Land (Antarctica). Isotopic differences in δ 202 Hg between MeHg and Hg(Sec)4 (−4.1 ± 0.1 ‰) reflect mass-dependent fractionation from a kinetic isotope effect due to the MeHg → Hg(Sec)4 demethylation reaction. Surprisingly, Hg(Sec)4 and HgSe differed isotopically in δ 202 Hg (+1.6 ± 0.1 ‰) and mass-independent anomalies (i.e., changes in Δ 199 Hg of ≤0.3 ‰), consistent with equilibrium isotope effects of massdependent and nuclear volume fractionation from Hg(Sec)4 → HgSe biomineralization. The invariance of species-specific δ 202 Hg values across tissues and individual birds reflects the kinetic lability of Hgligand bonds and tissue-specific redistribution of MeHg and inorganic Hg, likely as Hg(Sec)4. These observations provide fundamental information necessary to improve the interpretation of stable Hg isotope data and provoke a revisitation of processes governing isotopic fractionation in biota and toxicological risk assessment in wildlife. |
author2 |
Centre National de la Recherche Scientifique (CNRS) Institut des Sciences de la Terre (ISTerre) Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Université Savoie Mont Blanc (USMB Université de Savoie Université de Chambéry )-Centre National de la Recherche Scientifique (CNRS)-Université Gustave Eiffel-Université Grenoble Alpes (UGA) Upper Midwest Water Science Center U.S Geological Survey Centre d'Études Biologiques de Chizé - UMR 7372 (CEBC) La Rochelle Université (ULR)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE) LIttoral ENvironnement et Sociétés (LIENSs) La Rochelle Université (ULR)-Centre National de la Recherche Scientifique (CNRS) Department of Environmental Toxicology University of California (UC) |
format |
Article in Journal/Newspaper |
author |
Manceau, Alain Brossier, Romain Janssen, Sarah, E Rosera, Tylor, J Krabbenhoft, David, P Cherel, Yves Bustamante, Paco Poulin, Brett, A |
author_facet |
Manceau, Alain Brossier, Romain Janssen, Sarah, E Rosera, Tylor, J Krabbenhoft, David, P Cherel, Yves Bustamante, Paco Poulin, Brett, A |
author_sort |
Manceau, Alain |
title |
Mercury Isotope Fractionation by Internal Demethylation and Biomineralization Reactions in Seabirds: Implications for Environmental Mercury Science |
title_short |
Mercury Isotope Fractionation by Internal Demethylation and Biomineralization Reactions in Seabirds: Implications for Environmental Mercury Science |
title_full |
Mercury Isotope Fractionation by Internal Demethylation and Biomineralization Reactions in Seabirds: Implications for Environmental Mercury Science |
title_fullStr |
Mercury Isotope Fractionation by Internal Demethylation and Biomineralization Reactions in Seabirds: Implications for Environmental Mercury Science |
title_full_unstemmed |
Mercury Isotope Fractionation by Internal Demethylation and Biomineralization Reactions in Seabirds: Implications for Environmental Mercury Science |
title_sort |
mercury isotope fractionation by internal demethylation and biomineralization reactions in seabirds: implications for environmental mercury science |
publisher |
HAL CCSD |
publishDate |
2021 |
url |
https://hal.science/hal-03425602 https://hal.science/hal-03425602/document https://hal.science/hal-03425602/file/202Hg_Petrel_HAL.pdf https://doi.org/10.1021/acs.est.1c04388 |
genre |
Antarc* Antarctica Giant Petrels Kerguelen Islands |
genre_facet |
Antarc* Antarctica Giant Petrels Kerguelen Islands |
op_source |
ISSN: 0013-936X EISSN: 1520-5851 Environmental Science and Technology https://hal.science/hal-03425602 Environmental Science and Technology, 2021, 55 (20), pp.13942-13952. ⟨10.1021/acs.est.1c04388⟩ |
op_relation |
info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.est.1c04388 hal-03425602 https://hal.science/hal-03425602 https://hal.science/hal-03425602/document https://hal.science/hal-03425602/file/202Hg_Petrel_HAL.pdf doi:10.1021/acs.est.1c04388 |
op_rights |
info:eu-repo/semantics/OpenAccess |
op_doi |
https://doi.org/10.1021/acs.est.1c04388 |
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Environmental Science & Technology |
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55 |
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20 |
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13942 |
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13952 |
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1796946026933780480 |