In Vivo Formation of HgSe Nanoparticles and Hg–Tetraselenolate Complex from Methylmercury in Seabirds—Implications for the Hg–Se Antagonism
International audience In vivo and in vitro evidence for detoxification of methylmercury (MeHg) as insoluble mercury selenide (HgSe) underlies the central paradigm that mercury exposure is not or little hazardous when tissue Se is in molar excess (Se:Hg > 1). However, this hypothesis overlooks th...
Published in: | Environmental Science & Technology |
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Main Authors: | , , , , |
Other Authors: | , , , , , , , , , , , , |
Format: | Article in Journal/Newspaper |
Language: | English |
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HAL CCSD
2021
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Online Access: | https://hal.science/hal-03144114 https://hal.science/hal-03144114/document https://hal.science/hal-03144114/file/Article%20Petrel_HAL.pdf https://doi.org/10.1021/acs.est.0c06269 |
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Open Polar |
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Institut national des sciences de l'Univers: HAL-INSU |
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language |
English |
topic |
Mercury bird speciation selenoprotein P selenocysteine HR-XANES EXAFS STEM-HAADF STEM-EDX XANES STEM- [CHIM]Chemical Sciences |
spellingShingle |
Mercury bird speciation selenoprotein P selenocysteine HR-XANES EXAFS STEM-HAADF STEM-EDX XANES STEM- [CHIM]Chemical Sciences Manceau, Alain Gaillot, Anne-Claire Glatzel, Pieter Cherel, Yves Bustamante, Paco In Vivo Formation of HgSe Nanoparticles and Hg–Tetraselenolate Complex from Methylmercury in Seabirds—Implications for the Hg–Se Antagonism |
topic_facet |
Mercury bird speciation selenoprotein P selenocysteine HR-XANES EXAFS STEM-HAADF STEM-EDX XANES STEM- [CHIM]Chemical Sciences |
description |
International audience In vivo and in vitro evidence for detoxification of methylmercury (MeHg) as insoluble mercury selenide (HgSe) underlies the central paradigm that mercury exposure is not or little hazardous when tissue Se is in molar excess (Se:Hg > 1). However, this hypothesis overlooks the binding of Hg to selenoproteins, which lowers the amount of bioavailable Se that acts as a detoxification reservoir for MeHg, thereby underestimating the toxicity of mercury. This question was addressed by determining the chemical forms of Hg in various tissues of giant petrels Macronectes spp. using a combination of high energy-resolution X-ray absorption near edge structure and extended X-ray absorption fine structure spectroscopy, and transmission electron microscopy coupled to elemental mapping. Three main Hg species were identified, a MeHg-cysteinate complex, a four-coordinate selenocysteinate complex (Hg(Sec)4), and a HgSe precipitate, together with a minor dicysteinate complex Hg(Cys)2. The amount of HgSe decreases in the order liver > kidneys > brain = muscle, and the amount of Hg(Sec)4 in the order muscle > kidneys > brain > liver. On the basis of biochemical considerations and structural modeling, we hypothesize that Hg(Sec)4 is bound to the carboxy-terminus domain of selenoprotein P (SelP) which contains 12 Sec residues. Structural flexibility allows SelP to form multinuclear Hgx(Se,Sec)y complexes, which can be biomineralized to HgSe by protein self-assembly. Because Hg(Sec)4 has a Se:Hg molar ratio of 4:1, this species severely depletes the stock of bioavailable Se for selenoprotein synthesis and activity to one μg Se/g dry wet in the muscle of several birds. This concentration is still relatively high because selenium is naturally abundant in seawater, therefore it probably does not fall below the metabolic need for essential selenium. However, this study shows that this may not be the case for terrestrial animals, and that muscle may be the first tissue potentially injured by Hg ... |
author2 |
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) Institut des Matériaux Jean Rouxel (IMN) Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST) Université de Nantes (UN)-Université de Nantes (UN)-Ecole Polytechnique de l'Université de Nantes (EPUN) Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS) European Synchrotron Radiation Facility (ESRF) 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) Institut Universitaire de France (IUF) Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.) |
format |
Article in Journal/Newspaper |
author |
Manceau, Alain Gaillot, Anne-Claire Glatzel, Pieter Cherel, Yves Bustamante, Paco |
author_facet |
Manceau, Alain Gaillot, Anne-Claire Glatzel, Pieter Cherel, Yves Bustamante, Paco |
author_sort |
Manceau, Alain |
title |
In Vivo Formation of HgSe Nanoparticles and Hg–Tetraselenolate Complex from Methylmercury in Seabirds—Implications for the Hg–Se Antagonism |
title_short |
In Vivo Formation of HgSe Nanoparticles and Hg–Tetraselenolate Complex from Methylmercury in Seabirds—Implications for the Hg–Se Antagonism |
title_full |
In Vivo Formation of HgSe Nanoparticles and Hg–Tetraselenolate Complex from Methylmercury in Seabirds—Implications for the Hg–Se Antagonism |
title_fullStr |
In Vivo Formation of HgSe Nanoparticles and Hg–Tetraselenolate Complex from Methylmercury in Seabirds—Implications for the Hg–Se Antagonism |
title_full_unstemmed |
In Vivo Formation of HgSe Nanoparticles and Hg–Tetraselenolate Complex from Methylmercury in Seabirds—Implications for the Hg–Se Antagonism |
title_sort |
in vivo formation of hgse nanoparticles and hg–tetraselenolate complex from methylmercury in seabirds—implications for the hg–se antagonism |
publisher |
HAL CCSD |
publishDate |
2021 |
url |
https://hal.science/hal-03144114 https://hal.science/hal-03144114/document https://hal.science/hal-03144114/file/Article%20Petrel_HAL.pdf https://doi.org/10.1021/acs.est.0c06269 |
genre |
Giant Petrels |
genre_facet |
Giant Petrels |
op_source |
ISSN: 0013-936X EISSN: 1520-5851 Environmental Science and Technology https://hal.science/hal-03144114 Environmental Science and Technology, 2021, 55 (3), pp.1515-1526. ⟨10.1021/acs.est.0c06269⟩ |
op_relation |
info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.est.0c06269 hal-03144114 https://hal.science/hal-03144114 https://hal.science/hal-03144114/document https://hal.science/hal-03144114/file/Article%20Petrel_HAL.pdf doi:10.1021/acs.est.0c06269 |
op_rights |
info:eu-repo/semantics/OpenAccess |
op_doi |
https://doi.org/10.1021/acs.est.0c06269 |
container_title |
Environmental Science & Technology |
container_volume |
55 |
container_issue |
3 |
container_start_page |
1515 |
op_container_end_page |
1526 |
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1797583037171499008 |
spelling |
ftinsu:oai:HAL:hal-03144114v1 2024-04-28T08:19:39+00:00 In Vivo Formation of HgSe Nanoparticles and Hg–Tetraselenolate Complex from Methylmercury in Seabirds—Implications for the Hg–Se Antagonism Manceau, Alain Gaillot, Anne-Claire Glatzel, Pieter Cherel, Yves Bustamante, Paco 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) Institut des Matériaux Jean Rouxel (IMN) Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST) Université de Nantes (UN)-Université de Nantes (UN)-Ecole Polytechnique de l'Université de Nantes (EPUN) Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS) European Synchrotron Radiation Facility (ESRF) 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) Institut Universitaire de France (IUF) Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.) 2021-02-02 https://hal.science/hal-03144114 https://hal.science/hal-03144114/document https://hal.science/hal-03144114/file/Article%20Petrel_HAL.pdf https://doi.org/10.1021/acs.est.0c06269 en eng HAL CCSD American Chemical Society info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.est.0c06269 hal-03144114 https://hal.science/hal-03144114 https://hal.science/hal-03144114/document https://hal.science/hal-03144114/file/Article%20Petrel_HAL.pdf doi:10.1021/acs.est.0c06269 info:eu-repo/semantics/OpenAccess ISSN: 0013-936X EISSN: 1520-5851 Environmental Science and Technology https://hal.science/hal-03144114 Environmental Science and Technology, 2021, 55 (3), pp.1515-1526. ⟨10.1021/acs.est.0c06269⟩ Mercury bird speciation selenoprotein P selenocysteine HR-XANES EXAFS STEM-HAADF STEM-EDX XANES STEM- [CHIM]Chemical Sciences info:eu-repo/semantics/article Journal articles 2021 ftinsu https://doi.org/10.1021/acs.est.0c06269 2024-04-05T00:38:11Z International audience In vivo and in vitro evidence for detoxification of methylmercury (MeHg) as insoluble mercury selenide (HgSe) underlies the central paradigm that mercury exposure is not or little hazardous when tissue Se is in molar excess (Se:Hg > 1). However, this hypothesis overlooks the binding of Hg to selenoproteins, which lowers the amount of bioavailable Se that acts as a detoxification reservoir for MeHg, thereby underestimating the toxicity of mercury. This question was addressed by determining the chemical forms of Hg in various tissues of giant petrels Macronectes spp. using a combination of high energy-resolution X-ray absorption near edge structure and extended X-ray absorption fine structure spectroscopy, and transmission electron microscopy coupled to elemental mapping. Three main Hg species were identified, a MeHg-cysteinate complex, a four-coordinate selenocysteinate complex (Hg(Sec)4), and a HgSe precipitate, together with a minor dicysteinate complex Hg(Cys)2. The amount of HgSe decreases in the order liver > kidneys > brain = muscle, and the amount of Hg(Sec)4 in the order muscle > kidneys > brain > liver. On the basis of biochemical considerations and structural modeling, we hypothesize that Hg(Sec)4 is bound to the carboxy-terminus domain of selenoprotein P (SelP) which contains 12 Sec residues. Structural flexibility allows SelP to form multinuclear Hgx(Se,Sec)y complexes, which can be biomineralized to HgSe by protein self-assembly. Because Hg(Sec)4 has a Se:Hg molar ratio of 4:1, this species severely depletes the stock of bioavailable Se for selenoprotein synthesis and activity to one μg Se/g dry wet in the muscle of several birds. This concentration is still relatively high because selenium is naturally abundant in seawater, therefore it probably does not fall below the metabolic need for essential selenium. However, this study shows that this may not be the case for terrestrial animals, and that muscle may be the first tissue potentially injured by Hg ... Article in Journal/Newspaper Giant Petrels Institut national des sciences de l'Univers: HAL-INSU Environmental Science & Technology 55 3 1515 1526 |