A spectroscopic study of uranyl speciation in chloride-bearing solutions at temperatures up to 250 °C

Migdisov, A. A.; Boukhalfa, H.; Timofeev, A.; Runde, W.; Roback, R.; Williams-Jones, A. E.

doi:10.1016/j.gca.2017.10.016

Title: A spectroscopic study of uranyl speciation in chloride-bearing solutions at temperatures up to 250 °C

Journal Article · Tue Oct 24 00:00:00 EDT 2017 · Geochimica et Cosmochimica Acta

DOI:https://doi.org/10.1016/j.gca.2017.10.016· OSTI ID:1406219

^[1];

^[1]; Timofeev, A. ^[2]; Runde, W. ^[1];

^[1]; Williams-Jones, A. E. ^[2]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
McGill Univ., Montreal, QC (Canada). Dept. of Earth and Planetary Sciences

The speciation of U in NaCl-bearing solutions at temperatures up to 250 °C and concentrations of NaCl up to 1.5 m has been investigated using an in situ spectroscopic technique. The recorded spectra permit us to identify the species present in the solutions as UO₂²⁺, UO₂Cl⁺, and UO₂Cl₂°. UO₂Cl₃^- is also likely present at high temperatures and NaCl concentrations, but concentrations of this species are insufficient for derivation of the formation constants. No evidence was found for species of higher ligand (Cl-) number. Thermodynamic stability constants derived for these species show fair agreement with published data for 25 °C, but differ significantly from those predicted by an earlier high-temperature study (Dargent et al., 2013), which suggested that UO₂Cl₄^2- and UO₂Cl₅^3- contribute significantly to the mass balance of uranyl chloride complexes, especially at high temperature. In contrast, our data suggest that the main uranyl-chloride complex present in aqueous solutions at T >150 °C and concentrations of NaCl relevant to natural hydrothermal systems is UO₂Cl₂°. The values of the logarithms of thermodynamic formation constants (β) for the reaction UO₂²⁺ + Cl^- = UO₂Cl⁺ are 0.02, 0.25, 0.55, 1.09, 1.59, and 2.28 derived at 25, 50, 100, 150, 200, and 250 °C, respectively. For the reaction UO₂²⁺ + 2Cl^- = UO₂Cl₂° the values of log β derived at these temperatures are 0.4, 0.58, 0.74, 1.44, 2.18, and 3.42. Values of the formation constant estimated for uranyl-chloride species predict the high concentrations of U observed by Richard et al. (2011) in fluid inclusions of the giant McArthur River unconformity-type uranium deposit.

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

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE)

Grant/Contract Number:: AC52-06NA25396

OSTI ID:: 1406219

Alternate ID(s):: OSTI ID: 1635277

Report Number(s):: LA-UR-17-23808; TRN: US1702906

Journal Information:: Geochimica et Cosmochimica Acta, Vol. 222; ISSN 0016-7037

Publisher:: The Geochemical Society; The Meteoritical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 27 works

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Uranium transport in acidic brines under reducing conditions Timofeev, Alexander; Migdisov, Artaches A.; Williams-Jones, Anthony E. Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-03564-7	journal	April 2018

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