The solubility of La hydroxide and stability of La3+ and La hydroxyl complexes at acidic to mildly acidic pH from 25 to 250 °C

Abstract

The mobility of rare earth elements (REE) in natural hydrothermal systems can be assessed using geochemical modeling, which requires reliable thermodynamic data of relevant aqueous species. In this study, we evaluate the controls of pH and temperature on La speciation and the role of hydroxyl complexes in REE transport at hydrothermal conditions. Batch-type hydrothermal solubility experiments were conducted using synthetic La hydroxide powders equilibrated in perchloric acid-based aqueous solutions at temperatures between 150 and 250 °C and starting pH of 2 to 5. The La hydroxide solubility is retrograde with temperature and displays a strong pH dependence with a decrease in La concentrations from acidic to mildly acidic pH spanning between 3 and 5 orders of magnitude (e.g. log La molality of −2.5 to −7.2 at 250 °C). Thermodynamic optimizations using GEMSFITS allow to retrieve the standard partial molal Gibbs energies for the La3+ aqua ion and the formation constants for the La hydroxyl species (i.e., LaOH2+, La(OH)2+, La(OH)30) between 25 and 250 °C. A comparison between the experimentally derived thermodynamic properties with the calculated values from the Helgeson-Kirkham-Flowers equation of state parameters indicates an increased divergence with temperature. Discrepancies in standard partial molal Gibbs energies range between ∼ 1 − 12 kJ/mol and result in a predicted La hydroxide solubility differing by up to 3 orders of magnitude at 250 °C. Speciation calculations indicate a higher stability of La3+ and LaOH2+ over the other La hydroxyl species in the studied pH range of 3.4 to 6. The optimized thermodynamic properties for La aqueous species have important implications for modeling the solubility of REE minerals such as monazite and the mobility of REE in hydrothermal systems.