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This contribution presents a thermodynamic model revealing the mechanisms responsible for separation of Heavy and Light Rare Earth (HREE and LREE) phosphates in natural hydrothermal systems at temperatures of 250–350 °C. Our calculations were performed for an isothermal column of rock containing 0.5 wt% of apatite (Ca phosphate), which served as an immobilizing agent for REE dissolved in the solution. REE were transported by 10 wt% NaCl acidic solution. The model accounted for formation of REE phosphate solid solutions through a regular mixing model. It demonstrates that hydrothermal flushing can efficiently separate REE forming xenotime (HREE phosphate solid solutions) at the beginning of the column, and re-transportation of monazite (LREE rich) to the end of the column. This separation is primarily due to the fact that at elevated temperatures stability LREE chloride complexes is significantly higher than that for HREE. The model also evaluates behavior of U and Th, which accompany REE in vast majority of natural locations. It was found that U strongly fractionates to xenotime, whereas Th fractionates to monazite. This phenomenon can be explained by the differences in crystal-chemical characteristics between monazite and xenotime, and the mobility of Th in aqueous solutions at elevated temperatures.

Recent interest in U3Si2 as an advanced light water reactor fuel has driven assessment of numerous properties, but characterization of its response to H2O environments is sparse in available literature. The behavior of U3Si2 in H2O containing atmospheres is investigated and presented in a two-part series of articles. This work examines the behavior of U3Si2 following exposure to pressurized H2O at temperatures from 300 to 350 °C. Testing was performed using two autoclave configurations and multiple redox conditions. Use of solid state buffers to attain a controlled water chemistry is also presented as a means to test actinide-bearing systems. Buffers were used to vary the hydrogen concentration between 1 and 30 parts per million H2. Testing included UN, U3Si5, and UO2. Both UN and U3Si5 were found to rapidly pulverize in less than 50 h at 300 °C. Uranium dioxide was included as a control for the autoclave system, and was found to be minimally impacted by exposure to pressurized water at the conditions tested for extended time periods. Testing of U3Si2 at 300 °C found reasonable stability through 30 days in 1–5 ppm H2. However, pulverization was observed following 35 days. The redox condition of testing strongly affected pulverization. Characterization of the resulting microstructures suggests that the mechanism responsible for pulverization under more strongly reducing conditions differs from that previously identified. Hydride formation is hypothesized to drive this transition. Testing performed at 350 °C resulted in rapid pulverization of U3Si2 in under 50 h.

Carbon dioxide (CO2) is a major component of volcanic gases and ore-forming hydrothermal fluids. However, CO2 has contrasting effects on the speciation of different metal complexes and ore mineral solubility, but a molecular understanding of its effects is lacking. To address this deficiency, we conducted ab initio molecular dynamics (MD) simulations of the behavior of AuCl(aq) in the CO2–H2O system at 340 °C and 118–152 bar and 800 °C and 265–291 bar for CO2 mole fractions (XCO2) of 0.1–0.9. The MD simulations indicate that the linear [H2O–Au–Cl]0 structure of gold chloride is not affected by CO2 at XCO2 up to 0.8 at 340 °C and XCO2 up to 0.5 at 800 °C, whereas the “dry” [AuCl]0 species predominates at XCO2 > 0.8 at 340 °C and XCO2 > 0.5 at 800 °C. The number of water molecules hydrating the AuCl(aq) complex decreases systematically with an increasing CO2 mole fraction and increasing temperature. Results of Au solubility experiments at 340 °C in CO2–H2O solutions show that the addition of CO2 does not en...

The solubility of Nb2O5 and the speciation of niobium in HF-bearing aqueous solutions have been determined at temperatures of 150, 200, and 250 °C and saturated water pressure. At a pH of ∼2 and at low HF concentration, niobium is transported primarily as the species Nb(OH)4+ and at high HF concentration, as the species NbF2(OH)3°. Equilibrium constants for the formation of Nb(OH)4+ range from −11.23 ± 0.26 to −10.86 ± 0.24 and for the formation of NbF2(OH)3° from −3.84 ± 0.20 to −5.08 ± 0.42, at 150 and 250 °C. The results of this study show that the solubility of Nb2O5 (solid) in aqueous fluids increases with increasing HF concentration, but is not strongly affected by temperature. The influence of pH is variable; at low pH and HF concentration, a decrease in pH increases the solubility of Nb2O5 (solid). At higher pH, the reverse may be true. Modeling of the transport and deposition of niobium suggests that simple mixing with a brine is not an effective method for removing niobium from solution. By contrast, interaction of an acidic fluid with carbonate rock results in a rapid reduction in the capacity of the fluid to mobilize niobium.

For many years, our understanding of the behavior of the REE in hydrothermal systems was based on semi-empirical estimates involving extrapolation of thermodynamic data obtained at 25 °C (Haas et al., 1995; Wood, 1990a). Since then, a substantial body of experimental data has accumulated on the stability of aqueous complexes of the REE. These data have shown that some of the predictions of Haas et al. (1995) are accurate, but others may be in error by several orders of magnitude. However, application of the data in modeling hydrothermal transport and deposition of the REE has been severely hampered by the lack of data on the thermodynamic properties of even the most common REE minerals. The discrepancies between the predictions of Haas et al. (1995) and experimental determinations of the thermodynamic properties of aqueous REE species, together with the paucity of data on the stability of REE minerals, raise serious questions about the reliability of some models that have been proposed for the hydrothermal mobility of these critical metals. In this contribution, we review a body of high-temperature experimental data collected over the past 15 years on the stability of REE aqueous species and minerals. Using this new thermodynamic dataset, we re-evaluate the mechanisms responsible for hydrothermal transport and deposition of the REE. We also discuss the mechanisms that can result in REE fractionation during their hydrothermal transport and deposition. Our calculations suggest that in hydrothermal solutions, the main REE transporting ligands are chloride and sulfate, whereas fluoride, carbonate, and phosphate likely play an important role as depositional ligands. In addition to crystallographic fractionation, which is based on the differing affinity of mineral structures for the REE, our models suggest that the REE can be fractionated hydrothermally due to the differences in the stability of the LREE and HREE as aqueous chloride complexes.

Magmatic systems host many types of ore deposits, including world-class deposits of copper and gold. Magmas are commonly an important source of metals and ore-forming fluids in these systems. In many magmatic-hydrothermal systems, low-density aqueous fluids, or vapours, are significant metal carriers. Such vapours are water-dominated shallowly, but fluxing of CO2-rich vapour exsolved from deeper magma is now recognised as ubiquitous during open-system magma degassing. Furthermore, we show that such CO2-fluxing leads to a sharp drop in element solubility, up to a factor of 10,000 for Cu, and thereby provides a highly efficient, but as yet unrecognised mechanism for metal deposition.

The Wicheeda carbonatite is a deformed plug or sill that hosts relatively high grade light rare earth elements (LREE) mineralization in the British Columbia alkaline province. It was emplaced within metasedimentary rocks belonging to the Kechika Group, which have been altered to potassic fenite near the intrusion and sodic fenite at greater distances from it. The intrusion comprises a ferroan dolomite carbonatite core, which passes gradationally outward into calcite carbonatite. The potentially economic REE mineralization is hosted by the dolomite carbonatite. Three types of dolomite have been recognized. Dolomite 1 constitutes the bulk of the dolomite carbonatite, dolomite 2 replaced dolomite 1 near veins and vugs, and dolomite 3 occurs in veins and vugs together with the REE mineralization. Carbon and oxygen isotope ratios indicate that the calcite carbonatite crystallized from a magma of mantle origin, that dolomite 1 is of primary igneous origin, that dolomite 2 has a largely igneous signature with a small hydrothermal component, and that dolomite 3 is of hydrothermal origin. The REE minerals comprise REE fluorocarbonates, ancylite-(Ce), and monazite-(Ce). In addition to dolomite 3, they occur with barite, molybdenite, pyrite, and thorite. Minor concentrations of niobium are present as magmatic pyrochlore in the calcite carbonatite. A model is proposed in which crystallization of calcite carbonatite preceded that of dolomite carbonatite. During crystallization of the latter, an aqueous-carbonic fluid was exsolved, which mobilized the REE as chloride complexes into vugs and fractures in the dolomite carbonatite, where they precipitated mainly in response to the increase in pH that accompanied fluid-rock interaction and, in the case of the REE fluorocarbonates, decreasing temperature. These fluids altered the host metasedimentary rock to potassic fenite adjacent to the carbonatite and, distal to it, they mixed with formational waters to produce sodic fenite.

Conventional wisdom holds that aqueous solutions are the only non-magmatic fluids capable of concentrating metals in the Earth’s crust. The role of hydrocarbons in metal concentration is relegated to providing geochemical barriers at which the metals are reduced and immobilised. Liquid hydrocarbons, however, are also known to be able to carry appreciable concentrations of metals, and travel considerable distances. Here we report the results of an experimental determination of bulk solubilities of Au, Zn, and U in a variety of crude oils at temperatures up to 300 °C and of the benchtop-scale transport experiments that simulate hydrocarbon-mediated re-deposition of Zn at 25–200 °C. It has been demonstrated that the metal concentrations obtained in solubility experiments are within the range of concentrations that are typically considered sufficient for aqueous fluids to form ore bodies. It has also been shown that Zn can be efficiently transported and re-deposited by hydrocarbons. These results provide direct evidence of the ability of natural crude oils to mobilise metals available in hydrocarbon-associated host rocks, and transport them in concentrations sufficient to contribute to ore-forming processes.