The solubility of thorium in carbonate-bearing solutions at hydrothermal conditions

Nisbet, Haylea Dawn; Migdissov, Artaches; Williams-Jones, A. E.; van Hinsberg, Vincent; Xu, Hongwu; Roback, Robert Clifford

doi:10.1016/j.gca.2021.04.035

The solubility of thorium in carbonate-bearing solutions at hydrothermal conditions

Journal Article · Wed May 05 00:00:00 EDT 2021 · Geochimica et Cosmochimica Acta

DOI:https://doi.org/10.1016/j.gca.2021.04.035· OSTI ID:1783537

^[1]; ^[2]; Williams-Jones, A. E. ^[3]; van Hinsberg, Vincent ^[3]; ^[2]; ^[2]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States); McGill Univ., Montreal, QC (Canada)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
McGill Univ., Montreal, QC (Canada)

Thorium mineralization is frequently hosted in carbonate-bearing rocks, and thorium commonly substitutes into the structures of carbonate-bearing minerals that have precipitated from or been modified by hydrothermal fluids. Given this common association, it is reasonable to consider the hypothesis that the presence of carbonate ligands in hydrothermal solutions promotes the transport of Th through the formation of stable aqueous complexes. Our ability to evaluate this hypothesis, however, is hindered by the lack of experimental data for Th-carbonate species at conditions beyond ambient. The low-temperature data indicate that carbonate is a strong complexing agent for Th. In this contribution, we investigate the solubility of Th in carbonate-bearing fluids relevant to natural systems (0.05–0.5 m NaHCO₃/Na₂CO₃; pH_T ~ 7.8–9.8) at elevated temperature (175–250 °C). We demonstrate that, in contrast to the behavior of Th at low temperature, the stability of Th-carbonate complexes is not sufficient for them to predominate at these conditions. Instead, the solubility of Th is governed by hydrolysis reactions. Under the experimental conditions investigated, the predominant hydroxyl complexes are Th(OH)₄⁰ and Th(OH)₅-. Furthermore, thermodynamic formation constants were derived for these species at the temperatures considered in our experiments (log β₄ = 43.34 and 44.31 at 175 and 200 °C, respectively, and log β₅ = 46.15 and 47.9 at 225 and 250 °C, respectively) to permit forward modeling of Th mobility in natural systems. Our study indicates that carbonate ions are unlikely to play a role in transporting Th in hydrothermal fluids. Summarizing the results of this study and our previous studies of the solubility of Th in hydrothermal fluids, we conclude that SO₄^2- is the primary ligand responsible for the hydrothermal transport of Th.

View Accepted Manuscript (DOE)

Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE; USDOE Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: 89233218CNA000001

OSTI ID:: 1783537

Alternate ID(s):: OSTI ID: 1868583

Report Number(s):: LA-UR--20-30269

Journal Information:: Geochimica et Cosmochimica Acta, Journal Name: Geochimica et Cosmochimica Acta Vol. 330; ISSN 0016-7037

Publisher:: Elsevier; The Geochemical Society; The Meteoritical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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The solubility of thorium in carbonate-bearing solutions at hydrothermal conditions

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