Chemical Textures on Rare Earth Carbonates: An Experimental Approach to Mimic the Formation of Bastnäsite.

The interaction between multi-component rare earth element (REE) aqueous solutions and carbonate grains (dolomite, aragonite, and calcite) are studied at hydrothermal conditions (21-210 °C). The effect of ionic radii of five REEs (La, Ce, Pr, Nd, Dy) on solid formation are analyzed using two solution types: equal REE concentrations and concentrations normalized to Post Archean Australian Shale Standard (PAAS). The interaction replaces the host Ca-Mg carbonate grains with a series of REE minerals (lanthanite → kozoite → bastnäsite → cerianite). At 165 °C, equal concentration solutions promote kozoite crystallization, maintaining similar REE ratios in solids and solution. PAAS solutions result in zoned REE-bearing crystals with heterogeneous elemental distributions and discreet REE phases (e.g., cerianite). Chemical signatures indicate metastable REE-bearing phases transforming into more stable polymorphs, along with symplectite textures formed by adjacent phase reactions. Overall, experiments highlight the dependence of polymorph selection, crystallization pathway, mineral formation kinetics, and chemical texture on REE concentrations, ionic radii, temperature, time, and host grain solubility.

The role of fluocerite in the genesis of bastnäsite: mechanistic insights and transformation pathways.

Fluocerite is a rare earth element (REE) fluoride found as an accessory mineral in magmatic-hydrothermal REE ore deposits, including alkaline complexes and carbonatites, where it is often associated with REE-fluorocarbonates. This study investigates the crystallisation kinetics, mechanisms and energetics of fluocerite (REEF3) and its role as a precursor phase of bastnäsite, one of the key minerals used for the extraction of REE. Fluocerite was synthesized by reacting pure fluorite (CaF2) with La-, Ce- and Nd-bearing solutions at temperatures ranging from ambient to low hydrothermal (30-90 °C). The synthetic fluocerites were then placed in contact with Na2CO3 solutions at temperatures up to 200 °C. A combined approach using powder X-ray diffraction and scanning electron microscopy with energy dispersive spectroscopy was used to determine the nature and quantify the crystallising solids. Our findings reveal a temperature-dependent fluorite-fluocerite transformation, with completion observed within 1 hour at 90 °C and extending to around 30 days at 30 °C. The rate of crystallisation decreases proportionally with the atomic number of the rare earth elements. On the other hand, the carbonation reaction of fluocerite exhibits a significantly slower rate, by ∼3 orders of magnitude, in comparison to the fluorite-fluocerite transformation, regardless of temperature conditions. The synthetic La, Ce and Nd fluocerites transformed into bastnäsite at all temperatures, also forming cerianite (CeO2) in the Ce-bearing experiments and metastable kozoite, NdCO3OH(orth), in the Nd-bearing experiments. Activation energies of fluocerite nucleation increase proportionally with the ionic radii of the REE (81 ± 6 (La); 84 ± 5 (Ce), 96 ± 10 (Nd) kJ mol-1), while the activation energies associated with fluocerite crystallisation are slightly higher for La (90 ± 12 kJ mol-1) and similar for Ce and Nd (76 ± 12 and 72 ± 8 kJ mol-1, respectively).

Utilization of Eggshell Waste Calcite as a Sorbent for Rare Earth Element Recovery.

The green energy transition requires rare earth elements (REE) for the permanent magnets used in electric cars and wind turbines. REE extraction and beneficiation are chemically intensive and highly damaging to the environment. We investigated the use of eggshell waste as a sustainable alternative sorbent for the capture and separation of REE from aqueous solutions. Hen eggshell calcite was placed in multi-REE (La, Nd, Dy) solutions at 25 to 205 °C for up to 3 months. A pervasive diffusion of the REE inside the eggshell calcite was observed along pathways formed by the intracrystalline organic matrix and calcite crystal boundaries. At 90 °C, kozoite (REECO3OH, orthorhombic) spherulites precipitate on the surface of the dissolving calcite. At 165 and 205 °C, an interface-coupled dissolution-precipitation mechanism is observed, resulting in the complete dissolution of the calcite shell and its pseudomorphic replacement by polycrystalline kozoite. At 205 °C, kozoite is slowly replaced by hydroxylbastnäsite (REECO3OH, hexagonal), the stable form of the rare earth hydroxycarbonate polymorphs. Our results demonstrate two potential applications of eggshell waste for the uptake of rare earth elements in solution: at low temperatures, as a mixed organic-inorganic adsorbent and absorbent, given sufficient sorption time; and at higher temperatures, as an efficient sacrificial template for the precipitation of rare earth hydroxycarbonates.

Impact of Rare Earth Elements on CaCO3 Crystallization: Insights into Kinetics, Mechanisms, and Crystal Morphology.

This study investigated the crystallization kinetics and mechanisms of calcium carbonate (CaCO3) in the presence of rare earth elements (REEs) including lanthanum (La), neodymium (Nd), and dysprosium (Dy). Through a comprehensive approach utilizing UV-vis spectrophotometry, powder X-ray diffraction, and high-resolution electron microscopy, we examined the effects of REEs on CaCO3 growth from solution at varying concentrations and combinations of REEs. Our findings highlight that even trace amounts of REEs significantly decelerate the rate of CaCO3 crystallization, also leading to alterations in crystal morphology and mechanisms of growth. The impact of REEs becomes more pronounced at higher concentrations and atomic mass, although the potential formation of poorly ordered REEs carbonate precursor phases can result in a decrease in the REE3+/Ca2+ ratio, influencing the crystallization rate of CaCO3. Vaterite and calcite were identified as the main crystallized polymorphs, with vaterite exhibiting distinct growth defects and calcite developing complex morphologies at higher REEs concentrations and an internal architecture suggesting a nonclassical growth route. We propose that REEs ions selectively adsorb onto different calcite surfaces, impeding growth on specific sites and resulting in intricate morphologies.

The role of nanocerianite (CeO2) in the stability of Ce carbonates at low-hydrothermal conditions.

The formation of cerianite (CeO2) was investigated at low hydrothermal conditions (35-205 °C) via two experimental settings: (1) crystallisation from solution experiments, and (2) replacement of Ca-Mg carbonates (calcite, dolomite, aragonite) mediated by Ce-bearing aqueous solutions. The solid samples were studied with a combination of powder X-ray diffraction, scanning electron microscopy, and Fourier-transform infrared spectroscopy. The results revealed a multi-step crystallisation pathway: amorphous Ce carbonate → Ce-lanthanite [Ce2(CO3)3·8H2O] → Ce-kozoite [orthorhombic CeCO3(OH)] → Ce-hydroxylbastnasite [hexagonal CeCO3(OH)] → cerianite [CeO2]. We found that Ce carbonates can decarbonise in the final stage of the reaction, forming cerianite which significantly increases the porosity of the solids. The redox behaviour of Ce combined with the temperature, and the availability of CO2 3- govern this crystallisation sequence, the sizes, morphologies, and crystallisation mechanisms of the solid phases. Our results explain the occurrence and behaviour of cerianite in natural deposits. These findings also present a simple, environmental-friendly, and cost-efficient method for the synthesis of Ce carbonates and cerianite with tailored structures and chemistries.