15 Search Results

The rare earth elements (REE) are important for the green-energy transition and can be incorporated into the REE phosphates, such as xenotime-(Y), which also hosts heavy REE (Tb– Lu). Xenotime-(Y) is a common accessory mineral in metamorphic rocks and a range of mineral deposits where it controls the mobility of heavy REE, however, the impact of high temperature aqueous fluids on the behavior of heavy REE is largely unknown. Thermodynamic modeling can be utilized as a tool to predict the mobility of REE in hydrothermal aqueous fluids, but must be supported by accurate experimental data. Here, we measured the solubilitymore » of endmember synthetic xenotime-structured ErPO4 in NaCl-HCl-NaOH-bearing aqueous solutions at 350 °C and water vapor saturation pressure, at 400 and at 450 °C and 500 bar using batch-type Inconel reactors. Erbium speciation was investigated as a function of pH from 2.8 to 8, where Er chloride species are predominant at acidic conditions (pH <3) and Er hydroxyl complexes are predominant at near- neutral to alkaline conditions (pH >3). At pH 7–9, the measured ErPO₄ solubility (-9.8 to -7.5 log m_Er) is up to 2.5 orders of magnitude lower than thermodynamic predictions (-9.4 to -6.7 log m_Er) using existing thermodynamic databases. At pH 2–3, the predicted ErPO₄ solubility is ~0.5 orders of magnitude higher at 350 °C and ~1 order of magnitude lower at 450 °C compared to experimentally measured Er concentrations. The thermodynamic properties of aqueous Er species were therefore revised in this study. The partial molal Gibbs energy of formation (Δ_fG⁰_T,P) for aqueous Er hydroxyl and chloride species are optimized using GEMSFITS and the logarithmic formation constants (logβ_n(^Cl,OH)) were derived at each experimental temperature and pressure. The updated thermodynamic properties for Er hydroxyl species (Er(OH)⁺², Er(OH)₂⁺, and Er(OH)₃⁰) show that their stability shifts to more acidic conditions at and below 400 °C. The Er chloride species (ErCl⁺² and ErCl₂⁺) show increased stability compared to Er hydroxyl species at temperatures of 450 °C and 0.01 mol/kg NaCl. The updated thermodynamic properties are implemented into the GEM-Selektor modeling package to investigate the mobility of Er in saline hydrothermal fluids in equilibrium with alkaline rocks. Importantly, the updated properties for Er hydroxyl species result in low Er solubility at rock equilibrated pH conditions due to an expanded hydroxyl predominance zone, but lower aqueous complex stability overall, whereas previous models suggest greater stability for aqueous Er species. Furthermore, ErPO₄ solubility increases with decreasing temperature due to the deprotonation of HCl, which increases the acidity of hydrothermal fluids and the availability of Cl^- to complex with the REE. These simulations highlight how fluid-rock reaction and temperature affect the mobility of REE in hydrothermal ore-forming systems.« less

Dysprosium (Dy) is part of the heavy rare earth elements (REE) and a critical component in the production of high-performance super magnets used in wind turbines, electric vehicles, and other green technologies. The HREE phosphate, xenotime, is commonly associated with hydrothermal systems, where the mobility, fractionation, and deposition of REE are controlled by the stability of aqueous complexes and solubility of REE minerals which depend on temperature, pressure, and fluid composition (salinity, pH, and ligand availability). Here, we conducted a series of synthetic DyPO₄ solubility experiments in NaCl-HCl-bearing aqueous solutions (pH of 2 at 25 °C) from 500 to 700more » °C and 1.5 kbar using externally heated pressure vessels. DyPO₄ displays a strong prograde solubility with temperature across all studied fluid salinities (0–0.5 m NaCl). The DyPO₄ solubility isotherms at 500 °C, 600 °C, and 700 °C show a complex relationship with salinity where DyPO₄ solubility is highest (39.2–1552 ppm at 500–700 °C) in 0 m NaCl solutions, decreases strongly (21–331 ppm at 500–700 °C) in the 0.06 m NaCl solutions and remains relatively constant in the 0.25 m (42.8–248 ppm) and 0.5 m NaCl (40.2–124 ppm) solutions. Thermodynamic modeling suggests that pH increases as a function of temperature and salinity, and controls solubility due to the stability of chloride complexes (i.e., DyCl⁺² and DyCl₂⁺) at 500–600 °C, transitioning to hydroxyl complexes (i.e., Dy(OH)₃⁰) dominating at 700 °C and relatively alkaline pH. Comparison with NdPO₄ solubility data indicates that the light REE in monazite is significantly more soluble than the heavy REE in xenotime in saline fluids at high temperature (500–700 °C), implying efficient light/heavy REE fractionation in supercritical fluids. The lower solubility of DyPO₄ relative to NdPO₄ suggests that at high temperatures, acidic (pH 2–4), low-salinity (∼5 wt% NaCl) fluids will favor the precipitation of xenotime over monazite as it will cool from 700 °C to below 500 °C. These observations align with paragenetic mineral assemblages in NYF pegmatites (e.g., Baveno, Italy), where xenotime commonly immobilizes heavy REE during the high-temperature hydrothermal stages.« less

The hydrolysis of rare earth elements (REE) potentially controls their mobility during fluid-rock interaction in a broad range of pH and temperature conditions. However, there is still a lack of thermodynamic data for modeling accurately the stability of REE hydroxyl complexes in hydrothermal aqueous fluids. Here, in this study, UV–Vis spectrophotometric experiments were conducted from 25 to 75 °C in near-neutral to alkaline NaOH-bearing aqueous solutions with varying lanthanum (La) concentrations (0 to ∼0.23 mmol/kg). The color indicator m-cresol purple was used to determine in situ pH and derive the average OH− ligand number ($$\overrightarrow{n}$$) and formation constants for themore » La hydroxyl complexes (LaOH²⁺, La(OH)₂⁺, and La(OH)₃⁰). From 25 to 50 °C, $$\overrightarrow{n}$$ ranges between ∼1 and 2 at pH from 7.0 to 9.3. At 75 °C, $$\overrightarrow{n}$$ ranges between ∼1.5 and 3 at pH from 6.3 to 8.8. These results suggest the predominance of LaOH²⁺ and La(OH)₂⁺ complexes from 25 to 50 °C, and an increased predominance of La(OH)₃⁰ at 75 °C. The cumulative formation constants (β_n°, n = 1 to 3) are derived for the reaction La³⁺ + nOH⁻ = La(OH)_n^3-n, and fitted between 25 and 250 °C by combining the UV–Vis and literature solubility data. The resulting logβ_n° are expressed as function of temperature (T in Kelvin): logβ₁° = −1.786 + 0.0133 T + 1.049·10³/T; logβ₂° = −5.797 + 0.0267 T + 2.713·10³/T; logβ₃° = 6.435 + 0.0223 T + 512.7/T. A comparison between these new fits and existing extrapolations using the Helgeson-Kirkham-Flowers equation of state indicates significant differences in the predicted hydrolysis of La. The latter extrapolations should therefore be updated for the hydrolysis of REE.« less

The transport and enrichment of rare earth element (REE) ore bodies are dependent on the stability of aqueous metal ligand complexes and the solubility of REE bearing minerals. REE ores are commonly associated with igneous systems having aqueous fluids with high carbonate concentrations and REE solubilities have been shown to be dependent on temperature and associate anion aqueous ligands present in solution. Furthermore, this work presents solubility experiments of hydroxybastnäsite-(La) at elevated temperatures in aqueous solutions of varying carbonate concentrations. At lower temperatures, hydroxybastnäsite-(La) solubility is controlled by neutral mono-carbonate LaCO₃OH° but at higher temperatures and activities of carbonate species,more » charged di-carbonate La(CO₃)₂^- increases and predominates. This divergence, and the difference in solubility products of other hydroxybastnäsite-(REE) phases, provides a potential mechanism for REE fractionation in carbonate dominated aqueous solutions. To illustrate one such mechanism the solubility data of hydroxybastnäsite-(La) is compared with previously reported data of hydroxybastnäsite-(Nd) at elevated temperatures.« less

Aqueous speciation of rare earth elements (REE) controls their mobilization, fractionation, and enrichment in the natural waters. Geochemical modeling of their speciation is key to improve our understanding of the formation of economic mineral deposits, for developing mineral separation and mine tailing recovery technologies, and for characterizing the geochemistry of thermal water. However, our ability to predict the fate of REE in a wide pH and temperature range is limited by the scarcity of thermodynamic data for the REE hydroxyl complexes. In part I of this study (H. J. Han and A. P. Gysi, Dalton Trans., 2024, 53, 13129–13141), themore » optical properties of m-cresol purple (mCP) were determined using UV-Vis spectrophotometry between 25 and 75 °C in order to develop a method for deriving the hydrolysis constants of erbium (Er). Here, UV-Vis spectrophotometry experiments were conducted as a function of temperature between 35 and 75 °C to determine the hydrolysis of Er in near-neutral to alkaline solutions using mCP as an in situ pH color indicator. Here, the experiments were conducted with Er concentrations from 0 to ~0.253 mmol kg^–1 in low ionic strength solutions (≤0.001 mol kg^–1).« less

Acidic NaCl-rich aqueous fluids play a crucial role in forming hydrothermal rare earth elements (REE) mineral deposits. Aqueous REE mobility is mostly controlled by the stabilities of REE³⁺ and REE chloride species. Our current knowledge of REE speciation is based on solubility data, thermodynamic models and in situ spectroscopic measurements, sometimes coupled with molecular simulations. Here, in this study, we investigate Nd and Yb speciation in pH2 Cl-bearing solutions at 25 °C and 0.1 MPa with variable Cl/REE ratios using Raman Spectroscopy in solutions with 0.1 to 0.6 mol/kg NdCl₃ or YbCl₃ and 0.2 to 3.2 mol/kg NaCl. Due tomore » the challenges in resolving the REE-Cl band, we developed a new method using the water vibrational mode and multivariate curve resolution (MCR) analysis. The Raman spectra for the vibrational band of water (2700 to 3900 cm^–1) were collected at 25 °C and fitted by three Gaussian sub-peaks, then quantified using MCR analysis to de-convolute the water band into bulk H₂O and the perturbations caused by of Cl^–, REE³⁺, and REE chloride species. REE speciation based on the perturbations of the water band indicates that REE³⁺ aqua ions dominate acidic solutions at 25 °C, but up to ~20 mol% YbCl²⁺ forms at high YbCl₃ concentrations. The new method is promising for quantifying in situ speciation of the REE³⁺ aqua ions and REE chloride species in aqueous fluids while providing information on the hydration of ions. This method improves our molecular level understanding of REE aqueous species stability and their role in REE mobilization during fluid-rock interaction.« less

Raman spectroscopy provides a versatile tool for in situ characterization of aqueous rare earth elements (REE) speciation at the molecular level. Complexation of REE with ligands such as Cl^– and OH^– is of particular interest for understanding the mobility of REE in NaCl-bearing hydrothermal fluids responsible for enriching REE to economic levels in nature. Raman spectroscopic studies of REE speciation in Cl-bearing aqueous fluids are primarily conducted at ambient temperature, whereas natural systems indicate temperatures of >100–600 °C. In this study, the speciation of Dy in acidic chloride-bearing hydrothermal solutions was investigated using confocal Raman spectroscopy with a new capillarymore » Raman heating stage at 20–300 °C. Background solutions (pure water, NaCl-solutions) and solutions with 0.14–1.8 mol kg^–1 dissolved DyCl₃ were sealed in quartz capillary cells. Comparison of the spectra for Dy chloride solutions with those for background solutions and the spectra for reference Dy-bearing solids was used to identify Raman bands specific to Dy–O and Dy–Cl bonds. The Raman band for the Dy–O stretching mode of hydrated Dy³⁺ aqua ions was measured at 365–384 cm^–1 and a Raman band for the Dy–Cl stretching modes of Dy chloride complexes was measured near 240 cm^–1. The Dy–O band decreases systematically with temperature, whereas the Dy–Cl band systematically increases, indicating a systematic increase in the stability of Dy chloride complexes with temperature. Here, this study provides the framework for expanding the use of in situ Raman spectroscopy to investigate the speciation of REE in aqueous solutions to hydrothermal conditions.« less

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 decreasemore » 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. Here, 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.« less

The rare earth elements (REE) have important applications in green energy technologies. The formation of mineral deposits in geologic systems commonly involves hydrothermal fluids which can mobilize the REE. However, the REE speciation is not well known as a function of pH. The thermodynamic properties of REE hydroxyl complexes used in geochemical models are based on the Helgeson-Kirkham-Flowers (HKF) equation of state parameters which were derived by extrapolation of low temperature experimental and estimated data. In this study, Dy hydroxide solubility experiments are combined with available literature data to improve these models from 25 to 250 °C and optimize themore » thermodynamic properties of Dy³⁺ and Dy hydroxyl complexes using GEMSFITS. Batch-type solubility experiments were conducted from 150 to 250 °C and at saturated water vapor pressure in perchloric acid solutions with initial pH values of 2 to 5 in 0.5 pH unit increments. The measured solubility of Dy hydroxide is retrograde with temperature and decreases with pH. The logarithm of total dissolved Dy molality ranges from –2.3 to –5.3 at 150 °C (pH 4.7–5.5), from –2.4 to –5.6 at 200 °C (pH 3.9–5.1), and from –3.7 to –6.9 at 250 °C (pH of 3.4 and 5.0). The optimized standard partial molal Gibbs energies of formation (Δ_fG°_T) derived for Dy³⁺ and DyOH²⁺ display a close to linear relationship with temperature, fitting with previous optimizations based on DyPO₄ solubility data in the literature. A comparison of the optimized ΔfG°T values for aqueous Dy species with predictions from available HKF parameters indicates significant differences ranging from +11 to –26 kJ/mol between 25 and 250 °C. The experimental fits are used to derive the Dy hydroxide solubility products (K_s0) and formation constants for the hydrolysis of Dy (β_n with n = 1 to 3; Dy³⁺ + nOH^– = DyOH_n^3-n) as a function of temperature. The optimization method presented yields accurate thermodynamic properties for the Dy³⁺ aqua ions and the DyOH²⁺ species at the acidic to mildly acidic pH studied whereas more experimental work is needed at near-neutral and alkaline conditions to better constrain the other hydroxyl complexes. Furthermore, the optimized thermodynamic data have a significant impact on geochemical modeling of the mobility and solubility of REE minerals in acidic hydrothermal fluids.« less

A key aspect in the formation of rare earth elements (REE) deposits is the role of REE transport as aqueous REE complexes in supercritical hydrothermal solutions, where the nature of the aqueous complex is controlled by solution composition, temperature and pressure. Despite chloride being considered as one of the most abundant transporting ligands in magmatic-hydrothermal fluids, experimental investigations on the stability of aqueous REE chloride complexes are scarce above 300 °C. In this study, synthetic NdPO₄ crystals were reacted with non-saline and saline (0, 0.05 and 0.5 mNaCl), acidic (0.01 mHCl) aqueous solutions in a series of solubility experiments conductedmore » at 500–700 °C and 1.7 kbar, where the solubilities were determined using a stable Nd isotope (¹⁴⁵Nd isotope spike) dilution technique. NdPO₄ solubility ranges between 28 ppm and 10,858 ppm, where solubility increases with both temperature and salinity. At 500 °C, log mNdPO₄ increases from –3.93 to –1.60 and there is a strong correlation between NdPO₄ solubility and NaCl concentrations (slope of 1.2 ± 0.3), indicating stabilization of the Nd chloride aqueous complexes with a stoichiometry corresponding to NdCl²⁺. At 600 °C, this correlation is weaker (slope of 0.4, log mNdPO₄ increases from –2.63 to –1.88) indicating the stabilization of both Nd chloride and hydroxyl species controlling solubility. At 700 °C, NdPO₄ solubility is largely independent of NaCl concentration indicating that solubility is controlled by Nd hydroxyl complexes, where stoichiometry suggests the neutral Nd(OH)₃⁰ species is dominant. The solubility product (Ksp) of NdPO4 is derived from experimental data with the relation: log K_sp = -41.81 – 0.057T – 20987/T, with T temperature in Kelvin. Comparison of the measured Nd phosphate solubility to thermodynamic predictions using the available Helgeson-Kirkham-Flowers equation of state parameters for aqueous Nd complexes indicate that predictions are up to three orders of magnitude lower compared to experimental observations. This discrepancy is most pronounced in saline solutions, suggesting that thermodynamic properties of the REE chloride species in supercritical fluids require revision. Numerical simulations of fluid-rock interaction between acidic, saline fluids and a Strange Lake felsic mineral assemblage demonstrates that NdPO₄ solubility predictions from models are four to six orders of magnitude lower than those calculated based on empirical fits from experiments, which suggests that acidic, saline fluids may play an important role in mobilizing large amounts of light REE from 450 to 700 °C.« less