Sorption and catalytic oxidation of Fe(II) at the surface of calcite
International audience The effect of sorption and coprecipitation of Fe(II) with calcite on the kinetics of Fe(II) oxidation was investigated. The interaction of Fe(II) with calcite was studied experimentally in the absence and presence of oxygen. The sorption of Fe(II) on calcite occurred in two di...
Published in: | Geochimica et Cosmochimica Acta |
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Main Authors: | , , , |
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Format: | Article in Journal/Newspaper |
Language: | English |
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HAL CCSD
2009
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Online Access: | https://insu.hal.science/insu-00447473 https://doi.org/10.1016/j.gca.2009.01.003 |
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International audience The effect of sorption and coprecipitation of Fe(II) with calcite on the kinetics of Fe(II) oxidation was investigated. The interaction of Fe(II) with calcite was studied experimentally in the absence and presence of oxygen. The sorption of Fe(II) on calcite occurred in two distinguishable steps: (a) a rapid adsorption step (seconds–minutes) was followed by (b) a slower incorporation (hours–weeks). The incorporated Fe(II) could not be remobilized by a strong complexing agent (phenanthroline or ferrozine) but the dissolution of the outmost calcite layers with carbonic acid allowed its recovery. Based on results of the latter dissolution experiments, a stoichiometry of 0.4 mol% Fe:Ca and a mixed carbonate layer thickness of 25 nm (after 168 h equilibration) were estimated. Fe(II) sorption on calcite could be successfully described by a surface adsorption and precipitation model (Comans & Middelburg, GCA 51 (1987), 2587) and surface complexation modeling (Van Cappellen et al., GCA 57 (1993), 3505; Pokrovsky et al., Langmuir 16 (2000), 2677). The surface complex model required the consideration of two adsorbed Fe(II) surface species, >CO3Fe + and >CO 3FeCO3H 0. For the formation of the latter species, a stability constant is being suggested. The oxidation kinetics of Fe(II) in the presence of calcite depended on the equilibration time of aqueous Fe(II) with the mineral prior to the introduction of oxygen. If pre-equilibrated for >15 h, the oxidation kinetics was comparable to a calcite-free system (t1/2 = 145 ± 15 min). Conversely, if Fe(II) was added to an aerated calcite suspension, the rate of oxidation was higher than in the absence of calcite (t1/2 = 41 ± 1 min and t1/2 = 100 ± 15 min, respectively). This catalysis was due to the greater reactivity of the adsorbed Fe(II) species, >CO3FeCO3H 0, for which the species specific rate constant was estimated |
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Swiss Federal Insitute of Aquatic Science and Technology Dübendorf (EAWAG) Laboratoire de Géophysique Interne et Tectonophysique (LGIT) Observatoire des Sciences de l'Univers de Grenoble (OSUG) Université Joseph Fourier - Grenoble 1 (UJF)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut national des sciences de l'Univers (INSU - CNRS)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Savoie Mont Blanc (USMB Université de Savoie Université de Chambéry )-Centre National de la Recherche Scientifique (CNRS)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut national des sciences de l'Univers (INSU - CNRS)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Savoie Mont Blanc (USMB Université de Savoie Université de Chambéry )-Centre National de la Recherche Scientifique (CNRS)-Laboratoire Central des Ponts et Chaussées (LCPC)-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS) Faculty of Geosciences, UCEL Universiteit Utrecht / Utrecht University Utrecht funding by KTI, partial funding by RECOSY, partial funding by ANDRA and VENI grant #016.071.018 of NWO ANR-05-PCO2-0009,Geocarbone-CARBONATATION, Bio Minéralisation du carbone: de la caractérisation expérimentale à la modélisation(2005) |
format |
Article in Journal/Newspaper |
author |
Mettler, Suzanne Wolthers, Mariette Charlet, Laurent von Gunten, Urs |
spellingShingle |
Mettler, Suzanne Wolthers, Mariette Charlet, Laurent von Gunten, Urs Sorption and catalytic oxidation of Fe(II) at the surface of calcite |
author_facet |
Mettler, Suzanne Wolthers, Mariette Charlet, Laurent von Gunten, Urs |
author_sort |
Mettler, Suzanne |
title |
Sorption and catalytic oxidation of Fe(II) at the surface of calcite |
title_short |
Sorption and catalytic oxidation of Fe(II) at the surface of calcite |
title_full |
Sorption and catalytic oxidation of Fe(II) at the surface of calcite |
title_fullStr |
Sorption and catalytic oxidation of Fe(II) at the surface of calcite |
title_full_unstemmed |
Sorption and catalytic oxidation of Fe(II) at the surface of calcite |
title_sort |
sorption and catalytic oxidation of fe(ii) at the surface of calcite |
publisher |
HAL CCSD |
publishDate |
2009 |
url |
https://insu.hal.science/insu-00447473 https://doi.org/10.1016/j.gca.2009.01.003 |
genre |
Carbonic acid |
genre_facet |
Carbonic acid |
op_source |
ISSN: 0016-7037 EISSN: 0016-7037 Geochimica et Cosmochimica Acta https://insu.hal.science/insu-00447473 Geochimica et Cosmochimica Acta, 2009, 73 (7), pp.1826-1840. ⟨10.1016/j.gca.2009.01.003⟩ |
op_relation |
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.gca.2009.01.003 insu-00447473 https://insu.hal.science/insu-00447473 doi:10.1016/j.gca.2009.01.003 |
op_doi |
https://doi.org/10.1016/j.gca.2009.01.003 |
container_title |
Geochimica et Cosmochimica Acta |
container_volume |
73 |
container_issue |
7 |
container_start_page |
1826 |
op_container_end_page |
1840 |
_version_ |
1797581123278077952 |
spelling |
ftunigrenoble:oai:HAL:insu-00447473v1 2024-04-28T08:15:41+00:00 Sorption and catalytic oxidation of Fe(II) at the surface of calcite Mettler, Suzanne Wolthers, Mariette Charlet, Laurent von Gunten, Urs Swiss Federal Insitute of Aquatic Science and Technology Dübendorf (EAWAG) Laboratoire de Géophysique Interne et Tectonophysique (LGIT) Observatoire des Sciences de l'Univers de Grenoble (OSUG) Université Joseph Fourier - Grenoble 1 (UJF)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut national des sciences de l'Univers (INSU - CNRS)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Savoie Mont Blanc (USMB Université de Savoie Université de Chambéry )-Centre National de la Recherche Scientifique (CNRS)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut national des sciences de l'Univers (INSU - CNRS)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Savoie Mont Blanc (USMB Université de Savoie Université de Chambéry )-Centre National de la Recherche Scientifique (CNRS)-Laboratoire Central des Ponts et Chaussées (LCPC)-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS) Faculty of Geosciences, UCEL Universiteit Utrecht / Utrecht University Utrecht funding by KTI, partial funding by RECOSY, partial funding by ANDRA and VENI grant #016.071.018 of NWO ANR-05-PCO2-0009,Geocarbone-CARBONATATION, Bio Minéralisation du carbone: de la caractérisation expérimentale à la modélisation(2005) 2009-04-01 https://insu.hal.science/insu-00447473 https://doi.org/10.1016/j.gca.2009.01.003 en eng HAL CCSD Elsevier info:eu-repo/semantics/altIdentifier/doi/10.1016/j.gca.2009.01.003 insu-00447473 https://insu.hal.science/insu-00447473 doi:10.1016/j.gca.2009.01.003 ISSN: 0016-7037 EISSN: 0016-7037 Geochimica et Cosmochimica Acta https://insu.hal.science/insu-00447473 Geochimica et Cosmochimica Acta, 2009, 73 (7), pp.1826-1840. ⟨10.1016/j.gca.2009.01.003⟩ info:eu-repo/semantics/article Journal articles 2009 ftunigrenoble https://doi.org/10.1016/j.gca.2009.01.003 2024-04-18T02:41:50Z International audience The effect of sorption and coprecipitation of Fe(II) with calcite on the kinetics of Fe(II) oxidation was investigated. The interaction of Fe(II) with calcite was studied experimentally in the absence and presence of oxygen. The sorption of Fe(II) on calcite occurred in two distinguishable steps: (a) a rapid adsorption step (seconds–minutes) was followed by (b) a slower incorporation (hours–weeks). The incorporated Fe(II) could not be remobilized by a strong complexing agent (phenanthroline or ferrozine) but the dissolution of the outmost calcite layers with carbonic acid allowed its recovery. Based on results of the latter dissolution experiments, a stoichiometry of 0.4 mol% Fe:Ca and a mixed carbonate layer thickness of 25 nm (after 168 h equilibration) were estimated. Fe(II) sorption on calcite could be successfully described by a surface adsorption and precipitation model (Comans & Middelburg, GCA 51 (1987), 2587) and surface complexation modeling (Van Cappellen et al., GCA 57 (1993), 3505; Pokrovsky et al., Langmuir 16 (2000), 2677). The surface complex model required the consideration of two adsorbed Fe(II) surface species, >CO3Fe + and >CO 3FeCO3H 0. For the formation of the latter species, a stability constant is being suggested. The oxidation kinetics of Fe(II) in the presence of calcite depended on the equilibration time of aqueous Fe(II) with the mineral prior to the introduction of oxygen. If pre-equilibrated for >15 h, the oxidation kinetics was comparable to a calcite-free system (t1/2 = 145 ± 15 min). Conversely, if Fe(II) was added to an aerated calcite suspension, the rate of oxidation was higher than in the absence of calcite (t1/2 = 41 ± 1 min and t1/2 = 100 ± 15 min, respectively). This catalysis was due to the greater reactivity of the adsorbed Fe(II) species, >CO3FeCO3H 0, for which the species specific rate constant was estimated Article in Journal/Newspaper Carbonic acid Université Grenoble Alpes: HAL Geochimica et Cosmochimica Acta 73 7 1826 1840 |