Mercury Isotope Fractionation by Internal Demethylation and Biomineralization Reactions in Seabirds: Implications for Environmental Mercury Science
International audience A prerequisite for environmental and toxicological applicationsof mercury (Hg) stable isotopes in wildlife and humans is quantifyingthe isotopic fractionation of biological reactions. Here, we measured stableHg isotope values of relevant tissues of giant petrels (Macronectes s...
Published in: | Environmental Science & Technology |
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Online Access: | https://hal.archives-ouvertes.fr/hal-03401749 https://doi.org/10.1021/acs.est.1c04388 |
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ftccsdartic:oai:HAL:hal-03401749v1 2023-05-15T13:57:39+02:00 Mercury Isotope Fractionation by Internal Demethylation and Biomineralization Reactions in Seabirds: Implications for Environmental Mercury Science Manceau, Alain Brossier, Romain Janssen, Sarah Rosera, Tylor Krabbenhoft, David Cherel, Yves Bustamante, Paco Poulin, Brett Université Grenoble Alpes (UGA) Upper Midwest Water Science Center U.S Geological Survey Centre d'Études Biologiques de Chizé - UMR 7372 (CEBC) Université de La Rochelle (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 - UMRi 7266 (LIENSs) Université de La Rochelle (ULR)-Centre National de la Recherche Scientifique (CNRS) Department of Environmental Toxicology University of California 2021-10-19 https://hal.archives-ouvertes.fr/hal-03401749 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-03401749 https://hal.archives-ouvertes.fr/hal-03401749 doi:10.1021/acs.est.1c04388 ISSN: 0013-936X EISSN: 1520-5851 Environmental Science and Technology https://hal.archives-ouvertes.fr/hal-03401749 Environmental Science and Technology, American Chemical Society, 2021, 55 (20), pp.13942-13952. ⟨10.1021/acs.est.1c04388⟩ Mercury Isotope fractionation Toxicology Bird [SDE]Environmental Sciences info:eu-repo/semantics/article Journal articles 2021 ftccsdartic https://doi.org/10.1021/acs.est.1c04388 2021-10-30T22:25:32Z International audience A prerequisite for environmental and toxicological applicationsof mercury (Hg) stable isotopes in wildlife and humans is quantifyingthe isotopic fractionation of biological reactions. Here, we measured stableHg isotope values of relevant tissues of giant petrels (Macronectes spp.).Isotopic data were interpreted with published HR-XANES spectroscopic datathat document a stepwise transformation of methylmercury (MeHg) to Hgtetraselenolate(Hg(Sec)4) and mercury selenide (HgSe) (Sec =selenocysteine). By mathematical inversion of isotopic and spectroscopicdata, identical δ202Hg 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 eightbirds from the Kerguelen Islands and Adélie Land (Antarctica). Isotopicdifferences in δ202Hg between MeHg and Hg(Sec)4 (−4.1 ± 0.1‰) reflectmass-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 δ202Hg (+1.6 ± 0.1‰) and massindependentanomalies (i.e., changes in Δ199Hg of ≤0.3‰), consistent with equilibrium isotope effects of mass-dependent andnuclear volume fractionation from Hg(Sec)4 → HgSe biomineralization. The invariance of species-specific δ202Hg values acrosstissues and individual birds reflects the kinetic lability of Hg-ligand bonds and tissue-specific redistribution of MeHg and inorganicHg, likely as Hg(Sec)4. These observations provide fundamental information necessary to improve the interpretation of stable Hgisotope data and provoke a revisitation of processes governing isotopic fractionation in biota and toxicological risk assessment inwildlife. Article in Journal/Newspaper Antarc* Antarctica Giant Petrels Kerguelen Islands Archive ouverte HAL (Hyper Article en Ligne, CCSD - Centre pour la Communication Scientifique Directe) Kerguelen Kerguelen Islands Environmental Science & Technology 55 20 13942 13952 |
institution |
Open Polar |
collection |
Archive ouverte HAL (Hyper Article en Ligne, CCSD - Centre pour la Communication Scientifique Directe) |
op_collection_id |
ftccsdartic |
language |
English |
topic |
Mercury Isotope fractionation Toxicology Bird [SDE]Environmental Sciences |
spellingShingle |
Mercury Isotope fractionation Toxicology Bird [SDE]Environmental Sciences Manceau, Alain Brossier, Romain Janssen, Sarah Rosera, Tylor Krabbenhoft, David Cherel, Yves Bustamante, Paco Poulin, Brett Mercury Isotope Fractionation by Internal Demethylation and Biomineralization Reactions in Seabirds: Implications for Environmental Mercury Science |
topic_facet |
Mercury Isotope fractionation Toxicology Bird [SDE]Environmental Sciences |
description |
International audience A prerequisite for environmental and toxicological applicationsof mercury (Hg) stable isotopes in wildlife and humans is quantifyingthe isotopic fractionation of biological reactions. Here, we measured stableHg isotope values of relevant tissues of giant petrels (Macronectes spp.).Isotopic data were interpreted with published HR-XANES spectroscopic datathat document a stepwise transformation of methylmercury (MeHg) to Hgtetraselenolate(Hg(Sec)4) and mercury selenide (HgSe) (Sec =selenocysteine). By mathematical inversion of isotopic and spectroscopicdata, identical δ202Hg 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 eightbirds from the Kerguelen Islands and Adélie Land (Antarctica). Isotopicdifferences in δ202Hg between MeHg and Hg(Sec)4 (−4.1 ± 0.1‰) reflectmass-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 δ202Hg (+1.6 ± 0.1‰) and massindependentanomalies (i.e., changes in Δ199Hg of ≤0.3‰), consistent with equilibrium isotope effects of mass-dependent andnuclear volume fractionation from Hg(Sec)4 → HgSe biomineralization. The invariance of species-specific δ202Hg values acrosstissues and individual birds reflects the kinetic lability of Hg-ligand bonds and tissue-specific redistribution of MeHg and inorganicHg, likely as Hg(Sec)4. These observations provide fundamental information necessary to improve the interpretation of stable Hgisotope data and provoke a revisitation of processes governing isotopic fractionation in biota and toxicological risk assessment inwildlife. |
author2 |
Université Grenoble Alpes (UGA) Upper Midwest Water Science Center U.S Geological Survey Centre d'Études Biologiques de Chizé - UMR 7372 (CEBC) Université de La Rochelle (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 - UMRi 7266 (LIENSs) Université de La Rochelle (ULR)-Centre National de la Recherche Scientifique (CNRS) Department of Environmental Toxicology University of California |
format |
Article in Journal/Newspaper |
author |
Manceau, Alain Brossier, Romain Janssen, Sarah Rosera, Tylor Krabbenhoft, David Cherel, Yves Bustamante, Paco Poulin, Brett |
author_facet |
Manceau, Alain Brossier, Romain Janssen, Sarah Rosera, Tylor Krabbenhoft, David Cherel, Yves Bustamante, Paco Poulin, Brett |
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.archives-ouvertes.fr/hal-03401749 https://doi.org/10.1021/acs.est.1c04388 |
geographic |
Kerguelen Kerguelen Islands |
geographic_facet |
Kerguelen Kerguelen Islands |
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.archives-ouvertes.fr/hal-03401749 Environmental Science and Technology, American Chemical Society, 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-03401749 https://hal.archives-ouvertes.fr/hal-03401749 doi:10.1021/acs.est.1c04388 |
op_doi |
https://doi.org/10.1021/acs.est.1c04388 |
container_title |
Environmental Science & Technology |
container_volume |
55 |
container_issue |
20 |
container_start_page |
13942 |
op_container_end_page |
13952 |
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1766265429276229632 |