Liquid immiscibility in the system NaF–H<Subscript>2</Subscript>O and microlite solubility at 800°C

The NaF effect on microlite solubility at 800°C and 170, 200, and 230 MPa is studied experimentally. The immiscibility boundaries and compositions of fluid phases L₁ and L₂ are defined in the system NaF–H₂O at 800°C. It is established that microlite solubility increase in the L₁ phase, as compared with a homogeneous solution, is explained by the appearance in the L₁ phase of “free” HF in an amount of 0.025 ± 0.003 mol kg^–1 H₂O. The model of “acidification” L₁ and “alkalizing” L₂ is supposed.     

Uranium(VI) in aqueous solutions at 25°C and a pressure of 1 bar: Insight from experiments and calculations

The behavior of the 0.1 mNaCl + 0.002 mHCl + 1.9 × 10^?5 mUO₂(NO₃)₂ solution was studied at pH from 2.7 to 11.0, 25°C, and 1 bar in an argon atmosphere. The curve of variations in U concentration exhibits two minima at pH = 6.6 ± 0.7 and 10.0 ± 0.5. These minima are related to the precipitation of schoepite and clarkeite, respectively. The experimental data were used to refine the stability constants of U(VI) (hydroxo) complexes. For the polymer species of U(VI) with charges from +2 to ?1, the method of additivity of thermochemical increments was used, and increments of the linear relation were determined for the calculation of the Gibbs free energies of formation (Δ_fG _298.15 ⁰ ) of respective homologue series. The proposed method was applied to calculate the Δ_fG _298.15 ⁰ of formation of U(VI) (hydroxo)complexes containing from one to five uranium atoms.     

Hydrothermal synthesis of pyrochlores and their characterization

Pyrochlores, microlites, and U-betafites of pyrochlore group minerals were obtained from mixing experiments of the corresponding oxides and fluorides by hydrothermal synthesis at T = 800 °C and P = 200 MPa in the solution of 1.0 M NaF. The presence of U⁴⁺ in pyrochlore does not affect the cell parameter, which for the phases of pyrochlore–microlite series is 10.42 ± 0.01 Å. In a system with an excess of UO₂, pyrochlores and microlites, containing uranium up to 0.2–0.3 atoms per formula unit (apfu), are formed. In the uranium-free system of betafites composition, perovskites and Ti-bearing pyrochlores are formed. U-pyrochlores of betafite series, containing 2Ti = Nb + Ta in moles, have cubic cell parameters of 10.26 ± 0.02 Å and U⁴⁺ isomorphic capacity of 0.4–0.5 apfu. In the pyrochlore structure, U⁴⁺ may substitute for Ca²⁺ and Na⁺ cations in the eightfold site. In pyrochlores of pyrochlore–microlite series, Ca²⁺ is replaced by U⁴⁺, while in pyrochlores of betafite series, U⁴⁺ replaces Na⁺. Phases with pyrochlore structure, containing U⁵⁺ and U⁶⁺ in the sixfold site, usually occupied by Nb⁵⁺, Ta⁵⁺, and Ti⁴⁺, are formed under oxidizing conditions (Cu–Cu₂O buffer). They are characterized by low content of Nb⁵⁺, Ta⁵⁺ (<0.1 apfu), and anomalous behavior of the crystal lattice (compression, instead of expansion). Under natural conditions, the formation of pyrochlores containing a significant amount of U⁵⁺ and U⁶⁺ is unlikely.     

Interaction of model F-bearing silicic melt with chloride fluid,uraninite, and columbite at 750°C and 1000–2000 bar and its implications for estimation of the ore-forming capability of the upper crustal magma chamber beneath the Strel’tsovka caldera,eastern Transbaikalia

The experimental study of an F-bearing silicic melt—U, Nb, Ta minerals—chloride-fluoride fluid system is focused on ascertaining the origin of uranium deposits spatially related to intraplate silicic volcanism. The first series of experiments on uranium solubility in silicic melts close in composition to ore-bearing rhyolite of the unique Strel’tsovka Mo-U ore field has been performed in order to determine more precisely the ore genesis. As starting solid phases, model homogeneous glass of the chemical composition (wt %) 72.18 SiO₂, 12.19 Al₂O₃, 1.02 FeO, 0.20 MgO, 0.33 CaO, 4.78 Na₂O, 3.82 K₂O, 1.44 Li₂O, and 2.4 F (LiF, NaF, KF, CaF₂, MgF₂); synthetic UO₂ and UO₃·0.33H₂O; and natural columbite were used. The starting solutions contained 1.0 m Cl and 10⁻² m F. The runs were conducted in a gas vessel at a pressure of 1000 bar and in a high-pressure hydrothermal vessel at 2000 bar. The O₂ (H₂) fugacity was set by Ni-NiO, Co-CoO, Fe₃O₄-Fe₂O₃, and Cu-Cu₂O buffers. The equilibrium between melt and solution for major elements is reached during the first day, whereas 5–7 days are required for ore elements (U, Nb, Ta) to come into equilibrium. The solubility of Nb and especially Ta in Cl-F solutions equilibrated with F-bearing melt is extremely low. The solubility of U is much higher (10⁻⁴−10⁻⁵ mol/kg H₂O). The energy dispersive spectroscopy of run products allowed us to establish that columbite dissolved incongruently with formation of U- and F-bearing pyrochlores. The performed experiments have shown that a silicic melt close to the rhyolitic magma of the Strel’tsovka caldera in composition is not able to generate postmagmatic ore-forming solutions containing more than 10⁻⁶−10⁻⁵ mol U/kg H₂O under the relatively low pressure necessary for the existence of the first type of fluid. The amount of uranium that could have precipitated from this fluid in the zone of ore deposition is estimated at 216–9000 t. This estimate is two orders of magnitude lower than the total uranium resources of the deposits localized in the Strel’tsovka caldera. Thus, the upper crustal silicic magma chamber hardly was a source of uranium for Mo-U deposits of the Strel’tsovka ore field.     

Pyrochlores as indicators of the uranium-bearing potential of magmatic melts

The interaction of columbite and uraninite with a fluid-magma system consisting of a melt of Li-F-granite and fluoride fluid at 750°C and P = 2300 bar causes the formation of zonal pyrochlores being considerably different in uranium and fluorine contents. Fluorine-rich pyrochlores (to 7–12 at %) preserve the Nb/U ratio of the initial columbite (15–30). Uranium-bearing pyrochlores contain 2–4 times less amounts of fluorine, above 2 at % of uranium, and the Nb/U molar ratio decreases to 5–15. The analysis of Ca, U, and F variation trends points to the influence of temperature on the reactions of Ca²⁺ to U⁴⁺ cation exchange. The statistical analysis (250 measurements) showed that the maximum uranium content in pyrochlores amounted to 16 ± 5 wt % for the magmatic system saturated with uraninite.     

On the problem of transport species of tungsten by hydrothermal solutions

The solubility of pentatungstate of sodium (PTS) Na₂W₅O₁₆ · H₂O and sodium tungsten bronzes (STB) Na_0.16WO₃ in acid chloride solutions containing 0.026, 0.26, and 3.02m NaCl have been studied at 500°C, 1000 bar, given fO₂ (Co-CoO, Ni-NiO, PTS-STB buffers), and constant NaCl/HCl ratio (Ta₂O₅-Na₂Ta₄O₁₁ buffer). Depending on experimental conditions, the tungsten content in the solutions after experiments varied from 10⁻³ to 2 × 10⁻² mol/kg H₂O. Obtained data were used to calculate the formation constants of predominant tungsten complexes (VI, V): H₃W₃^VIO₁₂³⁻, W₃^VO₉³⁻, [W^VW₄^VIO₁₆]³⁻, for reactions

Pyrochlore Solubility in NaF Solutions at 800°C and p = 170–230 MPa

Doklady Earth Sciences - The solubility of pyrochlore (NaCa)Nb2O6F was studied experimentally in the NaF–H2O system covering both the homogeneous region of hydrothermal solutions and the...     

Study of the Behavior of Uranium,Niobium, and Tantalum in the Granite Melt–Fluoride Fluid System at 800–950°C, 2300 Bar

Geology of Ore Deposits - Experimental studies were carried out on the solubility of uranium, niobium, and tantalum in acidic melts of Li–F granites and predominantly fluoride fluids at...     

Research of the Uranium,Niobium, and Tantalum Behavior in the Granite Melt–Chloride Fluid System at 750°C and 1000 Bar

Geology of Ore Deposits - The major objective of the study investigation was to find the physicochemical conditions for U, Nb, and Ta mobilization into the solution from acidic melts similar in...