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Towards an understanding of thallium isotope fractionation during adsorption to manganese oxides

Towards an understanding of thallium isotope fractionation during adsorption to manganese oxides
Towards an understanding of thallium isotope fractionation during adsorption to manganese oxides
We have conducted the first study of Tl isotope fractionation during sorption of aqueous Tl(I) onto the manganese oxide hexagonal birnessite. The experiments had different initial Tl concentrations, amounts of birnessite, experimental durations, and temperatures, but all of them exhibit heavy Tl isotope compositions for the sorbed Tl compared with the solution, which is consistent with the direction of isotope fractionation observed between seawater and natural ferromanganese sediments. However, the magnitude of fractionation in all experiments (? ? 1.0002–1.0015, where ?=205Tl/203Tlsolid/205Tl/203Tlliq is smaller than observed between seawater and natural sediments (? ? 1.0019–1.0021; Rehkämper et al., 2002, Earth. Planet. Sci. Lett. 197, 65–81). The experimental results display a strong correlation between the concentration of Tl in the resulting Tl-sorbed birnessite and the magnitude of fractionation. This correlation is best explained by sorption of Tl to two sites on birnessite, one with large isotope fractionation and one with little or no isotope fractionation. Previous work (Peacock and Moon, 2012, Geochim. Cosmochim. Acta 84, 297–313) indicates that Tl in natural ferromanganese sediments is oxidized to Tl(III) and adsorbed over Mn vacancy sites in the phyllomanganate sheets of birnessite, and we hypothesize that this site is strongly fractionated from Tl in solution due to the change in oxidation state from aqueous Tl(I). In most experiments, which have orders of magnitude more Tl associated with the solid than in nature, these vacancy sites are probably fully saturated, so various amounts of additional Tl are likely sorbed to either edge sites on the birnessite or triclinic birnessite formed through oxidative ripening of the hexagonal starting material, with unknown oxidation state and little or no isotopic fractionation. Thus each experiment displays isotopic fractionation governed by the proportions of Tl in the fractionated and slightly fractionated sites, and those proportions are controlled by how much total Tl is sorbed per unit of birnessite. In the experiments with the lowest initial Tl concentrations in solution (?0.15–0.4 ?g/g) and the lowest concentrations of Tl in the resulting Tl-sorbed birnessite (?17 ?g Tl/mg birnessite), we observed the largest isotopic fractionations, and fractionation is inversely proportional to the initial aqueous Tl concentration. Again, this correlation can be explained by the simultaneous occupation of two different sorption sites; vacancy sites that carry isotopically fractionated Tl and a second site carrying slightly fractionated Tl. The fractionation factors observed in nature exceed those in the experiments likely because the Tl concentrations in seawater and in ferromanganese sediments are three to four orders of magnitude lower than in our experiments, and therefore the second slightly fractionated sorption site is not significantly utilized. Temperature (6–40 °C) and experimental duration (3 min–72 h) appear to have little or no effects on isotope behaviour in this system.
0016-7037
252-265
Nielsen, Sune G.
2754cef5-a4d1-408b-9467-987a42cb9385
Wasylenki, Laura E.
b26ebac4-593b-48a5-a596-e38d560f4327
Rehkämper, Mark
08591eef-a2d5-48de-9fc6-b5c0cf54f6e5
Peacock, Caroline L.
8a178011-0d4c-4fc3-867e-9883488c271f
Xue, Zichen
6acfcf55-4fd3-432e-a051-66a1929b6dc0
Moon, Ellen M.
63d6d6a1-3014-47a6-b701-1fdc5987a87c
Nielsen, Sune G.
2754cef5-a4d1-408b-9467-987a42cb9385
Wasylenki, Laura E.
b26ebac4-593b-48a5-a596-e38d560f4327
Rehkämper, Mark
08591eef-a2d5-48de-9fc6-b5c0cf54f6e5
Peacock, Caroline L.
8a178011-0d4c-4fc3-867e-9883488c271f
Xue, Zichen
6acfcf55-4fd3-432e-a051-66a1929b6dc0
Moon, Ellen M.
63d6d6a1-3014-47a6-b701-1fdc5987a87c

Nielsen, Sune G., Wasylenki, Laura E., Rehkämper, Mark, Peacock, Caroline L., Xue, Zichen and Moon, Ellen M. (2013) Towards an understanding of thallium isotope fractionation during adsorption to manganese oxides. Geochimica et Cosmochimica Acta, 117, 252-265. (doi:10.1016/j.gca.2013.05.004).

Record type: Article

Abstract

We have conducted the first study of Tl isotope fractionation during sorption of aqueous Tl(I) onto the manganese oxide hexagonal birnessite. The experiments had different initial Tl concentrations, amounts of birnessite, experimental durations, and temperatures, but all of them exhibit heavy Tl isotope compositions for the sorbed Tl compared with the solution, which is consistent with the direction of isotope fractionation observed between seawater and natural ferromanganese sediments. However, the magnitude of fractionation in all experiments (? ? 1.0002–1.0015, where ?=205Tl/203Tlsolid/205Tl/203Tlliq is smaller than observed between seawater and natural sediments (? ? 1.0019–1.0021; Rehkämper et al., 2002, Earth. Planet. Sci. Lett. 197, 65–81). The experimental results display a strong correlation between the concentration of Tl in the resulting Tl-sorbed birnessite and the magnitude of fractionation. This correlation is best explained by sorption of Tl to two sites on birnessite, one with large isotope fractionation and one with little or no isotope fractionation. Previous work (Peacock and Moon, 2012, Geochim. Cosmochim. Acta 84, 297–313) indicates that Tl in natural ferromanganese sediments is oxidized to Tl(III) and adsorbed over Mn vacancy sites in the phyllomanganate sheets of birnessite, and we hypothesize that this site is strongly fractionated from Tl in solution due to the change in oxidation state from aqueous Tl(I). In most experiments, which have orders of magnitude more Tl associated with the solid than in nature, these vacancy sites are probably fully saturated, so various amounts of additional Tl are likely sorbed to either edge sites on the birnessite or triclinic birnessite formed through oxidative ripening of the hexagonal starting material, with unknown oxidation state and little or no isotopic fractionation. Thus each experiment displays isotopic fractionation governed by the proportions of Tl in the fractionated and slightly fractionated sites, and those proportions are controlled by how much total Tl is sorbed per unit of birnessite. In the experiments with the lowest initial Tl concentrations in solution (?0.15–0.4 ?g/g) and the lowest concentrations of Tl in the resulting Tl-sorbed birnessite (?17 ?g Tl/mg birnessite), we observed the largest isotopic fractionations, and fractionation is inversely proportional to the initial aqueous Tl concentration. Again, this correlation can be explained by the simultaneous occupation of two different sorption sites; vacancy sites that carry isotopically fractionated Tl and a second site carrying slightly fractionated Tl. The fractionation factors observed in nature exceed those in the experiments likely because the Tl concentrations in seawater and in ferromanganese sediments are three to four orders of magnitude lower than in our experiments, and therefore the second slightly fractionated sorption site is not significantly utilized. Temperature (6–40 °C) and experimental duration (3 min–72 h) appear to have little or no effects on isotope behaviour in this system.

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Published date: 15 September 2013
Organisations: Ocean and Earth Science

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Local EPrints ID: 358776
URI: http://eprints.soton.ac.uk/id/eprint/358776
ISSN: 0016-7037
PURE UUID: 367a3908-b6de-4564-8e9b-e7e942d39df0

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Date deposited: 10 Oct 2013 12:40
Last modified: 27 Apr 2022 12:08

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Contributors

Author: Sune G. Nielsen
Author: Laura E. Wasylenki
Author: Mark Rehkämper
Author: Caroline L. Peacock
Author: Zichen Xue
Author: Ellen M. Moon

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