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In the field of actinide aqueous chemistry, this work aims to resolve some controversy about uranyl(VI) hydroxide species present in basic aqueous solutions. We revisit the Raman, IR, and UV-visible spectra with two new approaches. First, Raman, IR and UV data were recorded systematically from aqueous solutions with the noncomplexing electrolyte (C(2)H(5))(4)NNO(3) at 25 °C and 0.1 MPa ([U(total)] = 0.005-0.105 M) in H(2)O and D(2)O over a wide range of -log mH(D)(+) between 2.92 and 14.50. Second, vibrational spectra (IR and Raman) of basic solutions in H(2)O and D(2)O were analyzed using the Bayesian Positive Source Separation method to estimate pure spectra of individual species. In D(2)O solutions, the new spectroscopic data showed the occurrence of the same species as those in H(2)O. As observed for the wavenumber of the symmetric stretching mode, the wavenumber characteristic of the O═U═O antisymmetric stretching mode decreases as the number of OH(D)(-) ligands increases. These kinds of data, completed by (1) analysis of the signal widths, (2) persistence of the apparent exclusion rule between IR and Raman spectra of the uranyl species stretching modes, and (3) interpretation of the absorption UV-visible spectra, allow discussion of the chemistry, structures, and polynuclearity of uranyl(VI) species. In moderate basic solutions, the presence of two trimers is suggested. In highly basic solutions ([OH(-)] ≈ 3 M), the two monomers UO(2)(OH)(4)(2-) and UO(2)(OH)(5)(3-) are confirmed to be in good agreement with earlier EXAFS and NMR results. The occurrence of the UO(2)(OH)(6)(4-) monomer is also suggested from the more basic solutions investigated.

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The aim of this paper is to determine the physical and chemical parameters which control the opposite behaviour of uranium and tin-tungsten between 300° and 500 °C. In uranium deposits, fO2 and fS2 of mineralizing fluids are higher than values fixed by the pyrite-hematite-magnetite triple point, as shown by uraninite-hematite and/or pyrite mineral association. The stability of quartz-K feldspar-muscovite paragenesis in the wall-rocks of hydrothermal U deposits indicates weakly acid pH. By contrast, in the Sn-W occurrences from the French Southern Massif Central, the fO2 of mineralizing fluids is between Ni-NiO and Q-F-M buffers as shown by CO2-CH4-H2O-NaCl bearing fluid inclusions. The pH of these fluids is weakly acid to weakly basic as shown by the stability of muscovite in presence or absence of quartz and/or feldspar. Sn-W mineralizing fluids from Cornwall are by contrast purely aqueous and acid, as indicated by the mineral assemblage muscovite-quartz which is typical of greisens. Experimental data on UO2, SnO2, FeWO4, CaWO4 solubility and metal species in fluids show that fO2 > H-M are required for uranium transport whereas fO2 ≤ Ni-NiO favours Sn transport. The fluid oxidation state has no direct influence on the transport and deposition of tungsten. The fO2 control on the hydrothermal transport properties of these three metals is related on the one hand to the fluid and rock composition, and on the other hand to the minimal 320 °C temperature required for homogeneous equilibria in the C-O-H system to control the oxidation state at low values. At high temperatures, Sn, Fe and Ca chloride complexes are more stable than carbonate and phosphate uranium complexes ; this is attributable to their structure and to the dielectric content of the fluid. The presence of dissolved gases at high concentration, which are produced by devolatilization reactions at high temperatures, is emphasized since they lower the dielectric constant of the fluid which enhances the stability of chloride complexes. All these results show that temperature and fO2 account for the opposite behaviour of uranium and tin-tungsten in hydrothermal systems between 300° to 500 °C.