Rare Earth Elements Speciation Research Articles

Modeling rare earth elements binding to humic acids with model VII

Rare earth elements (REE) naturally occur at trace levels in natural systems but, due to their increasing use in modern technologies, they are now released into the environment, and considered as emerging contaminants. Therefore, the development of numerical predictive models of their speciation in various physico-chemical conditions is required to predict their behavior, transport and potentially toxic effects on ecosystems. Because REE speciation is largely affected by natural organic matter, such as humic acids (HA), this study aimed at calibrating an advanced humic-ion binding model (Model VII) to allow predicting REE-HA binding in various pH conditions, ionic strength and [REE]/[HA], as well as presence of competitor ions. First, REE complexation to monodentate O-containing ligands was evaluated using the Irving-Rossotti equation, which provided constraints for the optimization of REE-HA binding parameters for Model VII. Predictive capacities of Model VII were demonstrated by successfully modeling the effects of various cations (Al3+, Fe3+, Cu2+ and Ca2+) and carbonates on REE-HA binding. The large range of physico-chemical conditions for which Model VII is applicable suggest that the present model parameters might be used to more accurately predict the role played by NOM on REE speciation in very contrasting environments, such as in groundwaters, rivers, estuaries, seawater, soils or sediments. Therefore, this study provides a valuable numerical tool to predict the fate of REE in the environment.

Hydrothermal solubility of TbPO4, HoPO4, TmPO4, and LuPO4 xenotime endmembers at pH of 2 and temperatures between 100 and 250 °C

Rare earth element (REE) phosphates such as xenotime (YPO4) are important hosts to the heavy (H)REE in natural systems. Xenotime is commonly associated with hydrothermal alteration and mineral replacement reactions and its composition may yield important clues about the mineralization processes from aqueous fluids in critical mineral deposits. Robust underlying thermodynamic data for the REE phosphate endmembers and aqueous species are required to simulate the stability of xenotime and the mobility of REE in natural hydrothermal fluids. In this study, the solubility of synthetic TbPO4, HoPO4, TmPO4, and LuPO4 endmembers has been measured in aqueous solutions between 100 and 250 ∘C at saturated water vapor pressure. The solubility products (Ks0) determined in the experiments were compared to values retrieved from a combination of calorimetric data for the REE phosphates and thermodynamic properties of the aqueous REE species at elevated temperatures. The solubility of xenotime is retrograde and generally higher in the experiments than predicted by different sources of thermodynamic data. To resolve these discrepancies, the solubility data were used to optimize the thermodynamic properties of the REE phosphate endmembers and REE aqueous species. These optimizations permit retrieving a set of provisional standard Gibbs energies of formation for REE3+ and REEOH2+ at elevated temperature and were used to derive the following updated Ks0 values (uncertainty of ± 0.2 at the 95% confidence) for the reaction REEPO4 (s) = REE3+ + PO43−:Unlabelled Tablet (∘C)logKs0(TbPO4)logKs0(HoPO4)logKs0(TmPO4)logKs0 (LuPO4)100−27.3−27.7−27.9−28.1150−28.8−29.2−29.5−29.6200−30.6−30.9−31.2−31.4250−32.7−32.9−33.3−33.4The updated thermodynamic data generated from the solubility experiments have a significant impact on simulated xenotime compositions and predicted mobility of REE in crustal fluids. Future efforts are necessary to better constrain the properties of REE hydroxyl species at elevated temperature and possible non-ideal solid solution behavior for REE with ionic sizes significantly different from Y3+.

Characteristics of Some Selected Methods of Rare Earth Elements Recovery from Coal Fly Ashes

The article covers the issues related to the characteristics, application, and some methods of rare earth elements (REEs) recovery from coal fly ashes. REEs are elements with growing demand and a very wide range of application, especially when it comes to modern technologies. The conducted analysis and price forecast proved the existing upward tendency, and this confirmed the need to search for new REE sources, among industrial waste (proecological effect). The development of the REE recovery technology would involve solving several problems related to REE speciation, optimization of factors controlling their extractivity and selection of the REE separation method from obtained extraction solutions with a very extreme pH and complicated composition. The paper presented advantages and disadvantages of usually used methods of REE separation from coal fly ashes, like physical and acid–base leaching. It was also presented alternative REE recovery techniques in the form of membrane and biological methods and based on ion liquids (ILs) or chelating agents. The directions of further modifications, which will allow the efficient REE recovery were presented. The aim of this article was to propose specific solutions based on the creation of appropriate multistage method of REE recovery. It will be a combination of magnetic and size separation, acid–base leaching (including roasting in justified cases), removal of matrix elements with ILs (Al, Si, and Fe), and finally REE membrane separation, allowing one to obtain the appropriate process efficiency.

A study of rare earth ion-adsorption clays: The speciation of rare earth elements on kaolinite at basic pH

Synthesized rare earth ion-adsorption clays (La, Ce, Nd, Dy and Y, ~ 400 ppm each) were prepared from kaolinite at various basic pH in open-air conditions. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and inductively coupled plasma mass spectrometry (ICP-MS) were used to characterize the effect of pH on the adsorption mechanism of rare earth elements (REEs) on kaolinite. The crystal structure of kaolinite by XRD analysis is not altered after REE adsorption, suggesting that REEs are bound to the surface of kaolinite. Elemental analysis by XPS and ICP-MS show that the surface concentration of REEs on kaolinite is pH dependent, and a local maximum of the surface concentration is achieved at pH 10. Three characteristics of the La 3d5/2 XPS photoemission feature were measured and compared to those of standard La compounds to probe the speciation of REEs, and electrostatically bound hydroxides such as REE(OH)2+ are identified as the primary species on the surface of kaolinite. Compared to the typical ion-adsorption clays with intrinsic acidic pH, clays synthesized at basic pH exhibit similarly high rare earth ion-exchange efficiency with ammonium sulfate (AS), suggesting that rare earth ion-adsorption clays can exist in both acidic and basic environments.

Rare earth element distributions in rivers and sediments from the Erdenet Cu–Mo mining area, Mongolia

River water and sediments collected from the Erdenet, Gavil, and Khangal Rivers, near the Erdenet Cu–Mo mine were analyzed for their rare earth elements (REE) and yttrium (YREE) contents. Surface water samples were also collected from the tailing pond and ash pond of the mine, as well as in the seepage from the ash pond, where a part of the effluent flows into the Khangal river. The major chemical compositions of river and surface waters were found to vary slightly with water flow. The river water is Ca–HCO3-dominated in the upstream of the Erdenet and Gavil Rivers and ash pond; Ca–SO4-dominated in the tailing pond and seepage from the ash pond; and Ca–HCO3–SO4-dominated downstream of the Erdenet and Khangal Rivers. Both river and surface water exhibited a significant diatom content and the dissolved organic matter mainly comprise of fulvic acid-like materials, protein-like materials and microbial materials.The concentrations of YREE in river and surface waters ranged from 4.6 to 14.9 ng/L, whereas those of the sediments and rocks were 10–43 mg/kg and 25–34 mg/kg, respectively. Shale-normalized YREE patterns of river and surface waters, irrespective of water type, were characterized by enrichments in the middle REE (MREE) and heavy REE (HREE) relative to the light REE (LREE), exceptionally positive La anomalies, and super-chondritic Y/Ho ratios. The predominant REE species were REE(CO3)2−, REECO3+, and REESO4+ in the Ca–SO4-rich water. The HREE enrichment in both river and surface waters resulted in stronger complexation with carbonate ions and fulvic-acid like materials with increasing atomic number and preferential sorption of LREE onto sediments in neutral to slightly alkaline pH water. The YREE patterns of sediments showed MREE enrichment. Total YREE contents in the river sediments were correlated with Fe2O3, P2O5 and loss on ignition (LOI), suggesting the MREE enrichment fractionated by precipitation of authigenic MREE-enriched minerals such as phosphate, Fe (oxy)hydroxides and organic matter. With the exception of La, there were significant correlations among neighboring YREE concentrations, indicating that most YREEs were fractionated by the same geochemical processes, such as aqueous complexation and sorption onto the sediment surfaces. The concentrations of La did not correlate with those of the other YREE, suggesting that the La anomaly was probably induced by a biogenic activity such as diatom blooming and/or anthropogenic processes. Our results provide better understanding of REE behavior because of (bio)geochemical and anthropogenic contamination in terrestrial water systems.

Evaluation of selectivity of sequential extraction procedure applied to REE speciation in laterite

Rare earth elements (REE) speciation in laterites are commonly estimated from sequential extraction procedure (SEP). In this study, the selectivity of a 5-steps SEP protocol was evaluated on individual synthetic Ce-material and applied to a well-characterized lateritic profile developing over a granite bedrock (Madagascar). The synthetic Ce-materials are representative of laterite minerals: Ce-doped oxyhydroxides and kaolinite, cerianite, Ce-rhabdophane and Ce-bastnäsite. The morphology, specific surface area, Ce sorption concentrations were thoroughly characterized prior to SEP. X-Ray absorption spectroscopy on synthetic material indicates that Ce(III) dominates apart for cerianite and Mn-oxide. The evaluation of the 5-steps SEP scheme shows that reagent selectivity is generally good, but the use of hydroxylamine hydrochloride is strongly discouraged. First, distinction between Ce sorbed at the surface of Mn- and amorphous or crystalline Fe-oxyhydroxides remains ambiguous. Second, Ce-rhabdophane (phosphate) and Ce-bastnäsite (carbonate) dissolve partially with this reagent. These experimental results combined with previous mineralogical and geochemical characterization were fundamental to interpret SEP results in the laterite profile from Madagascar. In the three laterite samples from the A-, B- and C-horizons, it is proposed that REE mainly distribute in authigenic phosphates and Fe- and (Mn-)oxyhydroxides. In the oxidized B-horizon, there is a significant LREE/HREE and Ce(IV)/Ce(III) fractionation between laterite minerals. While LREE-Ce is mainly concentrated in phosphates (alunite-jarosite supergroup), it is proposed that HREE and Ce(IV) uptake is dominated by oxyhydroxides. In the A- and C-horizons, the LREE and HREE speciations are similar, indicating no significant LREE/HREE fractionation in laterite minerals and organic matter. In all horizons, the REE ion exchangeable is negligible, although kaolinite is a main mineral of the A- and B-horizons.

Adsorption of rare earth elements in regolith-hosted clay deposits

Global resources of heavy Rare Earth Elements (REE) are dominantly sourced from Chinese regolith-hosted ion-adsorption deposits in which the REE are inferred to be weakly adsorbed onto clay minerals. Similar deposits elsewhere might provide alternative supply for these high-tech metals, but the adsorption mechanisms remain unclear and the adsorbed state of REE to clays has never been demonstrated in situ. This study compares the mineralogy and speciation of REE in economic weathering profiles from China to prospective regoliths developed on peralkaline rocks from Madagascar. We use synchrotron X-ray absorption spectroscopy to study the distribution and local bonding environment of Y and Nd, as proxies for heavy and light REE, in the deposits. Our results show that REE are truly adsorbed as easily leachable 8- to 9-coordinated outer-sphere hydrated complexes, dominantly onto kaolinite. Hence, at the atomic level, the Malagasy clays are genuine mineralogical analogues to those currently exploited in China.

Local Structure of Rare Earth Elements (REE) in Marine Ferromanganese Oxides by Extended X-ray Absorption Fine Structure and Its Comparison with REE in Ion-adsorption Type Deposits

Speciation of rare earth elements (REE) in marine ferromanganese oxides (MFMO) was conducted by extended X-ray absorption fine structure (EXAFS) and sequential extraction to compare the enrichment ...

Thermodynamic Constraints on REE Mineral Paragenesis in the Bayan Obo REE-Nb-Fe Deposit, China

Hydrothermal processes have played a significant role in rare earth element (REE) precipitation in the Bayan Obo REE-Nb-Fe deposit. The poor preservation of primary fluid inclusions and superposition or modification by multiphase hydrothermal activities have made identification of physico-chemical conditions of ore-forming fluids extremely difficult. Fortunately, with more and more reliable thermodynamic properties of aqueous REE species and REE minerals reported in recent years, a series of thermodynamic calculations are conducted in this study to provide constraints on REE precipitation in hydrothermal solutions, and provide an explanation of typical paragenesis of REE and gangue minerals at Bayan Obo. During the competition between fluocerite and monazite for LREE in the modelled solution (0.1 M HCl, 0.1 M HF and 0.1 M trichloride of light rare earth elements (LREE) from La to Sm), all LREE would eventually be hosted by monazite at a temperature over 300 °C, with continuous introduction of H3PO4. Additionally, monazite of heavier LREE would precipitate earlier, indicating that the Ce- and La-enriched monazite at Bayan Obo was crystallized from Ce and La pre-enriched hydrothermal fluids. The fractionation among LREE occurred before the ore-forming fluids infiltrating ore-hosting dolomite. When CO2 (aq) was introduced to the aqueous system (model 1), bastnaesite would eventually and completely replace monazite-(Ce). Cooling of hot hydrothermal fluids (>400 °C) would significantly promote this replacement, with only about one third the cost of CO2 for the entire replacement when temperature dropped from 430 °C to 400 °C. Sole dolomite addition (model 2) would make bastnaesite replace monazite and then be replaced by parisite. The monazite-(Ce) replaced by associated bastnaesite and apatite is an indicator of very hot hydrothermal fluids (>400 °C) and specific dolomite/fluid ratios (e.g., initial dolomite at 1 kbar: 0.049–0.068 M and 0.083–0.105 M at 400 °C and 430 °C). In hot solution (>430 °C) that continuously interacts with dolomite, apatite precipitates predating the bastnaesite, but it behaves oppositely at <400 °C. The former paragenesis is in accord with petrography observed in this study. Some mineral pairs, such as monazite-(Ce)-fluorite and monazite-(Ce)-parisite would never co-precipitate at any calculated temperature or pressure. Therefore, their association implies multiphase hydrothermal activities. Pressure variation would have rather limited influence on the paragenesis of REE minerals. However, temperature and fluid composition variation (e.g., CO2 (aq), dolomite, H3PO4) would cause significantly different associations between REE and gangue minerals.

The solubility of monazite (LaPO4, PrPO4, NdPO4, and EuPO4) endmembers in aqueous solutions from 100 to 250 °C

Monazite is a light rare earth element (REE) phosphate found in REE mineral deposits, such as those formed in (per)alkaline and carbonatite magmatic-hydrothermal systems, where it occurs in association to the development of alteration zones and hydrothermal veins. Although it has been recognized that monazite may undergo replacement by coupled dissolution-precipitation processes, currently there is no model describing the compositional REE variations in monazite resulting from direct interaction with or precipitation from hydrothermal fluids. To develop such a model requires quantification of the thermodynamic properties of the aqueous REE species and the properties of the monazite endmembers and their solid solutions. The thermodynamic properties of monazite endmembers have been determined previously using calorimetric methods and low temperature solubility studies, but only a few solubility studies have been conducted at >100 °C. In this study, the solubility products (logKs0) of LaPO4, PrPO4, NdPO4, and EuPO4 monazite endmembers have been measured at temperatures between 100 and 250 °C and saturated water vapor pressure. The solubility products are reported with an uncertainty of ±0.2 (95% confidence) according to the reaction, REEPO4(s) = REE3+ + PO43−.▪The REE phosphates display a retrograde solubility, with the measured Ks0 values varying several orders of magnitude over the experimental temperature range. Discrepancies were observed between the experimental solubility products and the calculated values resulting from combining calorimetric data of monazite with the properties of the aqueous REE3+ and PO43− species available in the literature. The differences between the calculated and measured standard Gibbs energy of reaction (ΔrG0) for PrPO4, NdPO4, and EuPO4 increased with higher temperatures (up to 15 kJ mol−1 at 250 °C), whereas for LaPO4 these differences increased at lower temperatures (up to 8 kJ mol−1 at 100 °C). To reconcile these discrepancies, the standard enthalpy of formation (ΔfH0) of monazite was optimized by fitting the experimental solubility data and extrapolating these fits to reference conditions of 25 °C and 1 bar. The optimized thermodynamic data provide the first internally consistent dataset for the solubility of all the monazite endmembers, and can be used to model REE partitioning between monazite and hydrothermal fluids at >100 °C.

Speciation transformation of rare earth elements (REEs) during heating and implications for REE behaviors during coal combustion

The recovery of rare earth elements (REEs) from coal ash has gained growing attention as a promising resource recovery strategy. Compared to extensive studies on REE occurrence in coal and coal ash, few studies have investigated REE behaviors during coal combustion processes. This study investigated the mineralogy, oxidation state, and structure changes of twelve representative REE-bearing phases during heating up to 1500 °C using complementary thermal analysis, in-situ X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray absorption spectroscopy (XAS), in order to better understand and predict REE behaviors during coal combustion processes. It was found that: (1) REE-lignin and REE-chitosan complexes, hydrated Y2(CO3)3 and Ce2(CO3)3, bastnäsite, and REE-doped calcite transformed to corresponding oxides after heating, accompanied by Ce(III) oxidation; (2) hydrated YPO4 and CePO4 formed corresponding anhydrous REE phosphates after heating with no evident Ce(III) oxidation; and (3) apatite, monazite, xenotime, and zircon barely altered during heating, although Ce(III) in apatite was partially oxidized and Y local structure became more disordered in apatite, monazite, and zircon. These results are consistent with previous studies on REE speciation in coal and coal ash and provided an in-depth understanding on REE behaviors during coal combustion, including mineral transformations and retention of REE-bearing phases. XAS analysis revealed that due to the co-existence of different REEs, mineralogical changes, and local structural distortion of REE-bearing phases during combustion, quantification of REE speciation in coal ash using XAS should be interpreted with caution and cross-validated by other techniques.

Rare earth element and strontium isotope geochemistry in Dujiali Lake, central Qinghai-Tibet Plateau, China: Implications for the origin of hydromagnesite deposits

Rare earth element (REE) and strontium isotope data (87Sr/86Sr) are presented for hydromagnesite and surface waters that were collected from Dujiali Lake in central Qinghai-Tibet Plateau (QTP), China. The goal of this study is to constrain the solute sources of hydromagnesite deposits in Dujiali Lake. All lake waters from the area exhibit a slight LREE enrichment (average [La/Sm]PAAS = 1.36), clear Eu anomalies (average [Eu/Eu*]PAAS = 1.31), and nearly no Ce anomalies. The recharge waters show a flat pattern (average [La/Sm]PAAS = 1.007), clear Eu anomalies (average [Eu/Eu*] PAAS = 1.83), and nearly no Ce anomalies (average [Ce/Ce*]PAAS = 1.016). The REE+Y data of the surface waters indicate the dissolution of ultramafic rock at depth and change in the hydrogeochemical characteristics through fluid-rock interaction. These data also indicate a significant contribution of paleo-groundwater to the formation of hydromagnesite, which most likely acquired REE and Sr signatures from the interaction with ultramafic rocks. The 87Sr/86Sr data provide additional insight into the geochemical evolution of waters of the Dujiali Lake indicating that the source of Sr in the hydromagnesite does not directly derive from surface water and may have been influenced by both Mg-rich hydrothermal fluids and meteoric water. Additionally, speciation modeling predicts that carbonate complexes are the most abundant dissolved REE species in surface water. This study provides new insights into the origins of hydromagnesite deposits in Dujiali Lake, and contributes to the understanding of hydromagnesite formation in similar modern and ancient environments on Earth.

Comprehensive Understandings of Rare Earth Element (REE) Speciation in Coal Fly Ashes and Implication for REE Extractability.

In recent years, recovery of rare earth elements (REEs) from coal fly ashes (CFAs) has been considered as a promising resource recovery option. Yet, quantitative information on REE speciation in CFAs and its correlation with REE extractability are not well established. This study systematically investigated the REE speciation-extractability relationship in four representative CFA samples by employing multiple analytical and spectroscopic techniques across the micro to bulk scale and in combination with thermodynamic calculations. A range of REE-bearing phases are identified, such as REE oxides, REE phosphates, apatite, zircon, and REE-bearing glass phase. REEs can occur as discrete particles, as particles encapsulated in the glass phase, or distribute throughout the glass phase. Although certain discrepancies exist on the REE speciation quantified by X-ray adsorption spectroscopy and acid leaching due to intrinsic limitations of each method, both approaches show significant fractions of REE oxides, REE phosphates, apatite, and REE-bearing Fe oxides. This study contributes to an in-depth understanding of the REE speciation-distribution-extractability relationship in CFAs and can help identify uncertainties associated with the quantification of REE speciation. It also provides a general methodology for future studies on REE speciation in complex environmental samples and a knowledge basis for the development of effective REE recovery techniques.

Effect of Anions on the Solubility of Rare Earth Element-Bearing Minerals in Acids

The effect of anions such as sulfate, chloride, and nitrate on the solubility of rare earth element-bearing phosphates and fluoro-carbonates has been examined using relevant thermodynamic data. The study has found that these anions have significant influences on the overall dissolution of rare earth elements (REEs) from various sources in the aqueous media. The thermodynamic calculations in this study have indicated that the speciation of REEs with the anions tends to increase the overall solubility of the REE-bearing minerals. However, in some cases, strong precipitation of REEs with some of these anions causes an adverse effect on the solubility of these elements. It has been found that sulfate ion has the most pronounced effect on the solubility compared to nitrate and chloride, in which the latter two acids exhibited almost identical results. The calculated results have indicated that REE-oxide (hydrated) is the easiest compound to dissolve, followed by carbonate, phosphate, fluoride, sulfate, fluoro-carbonate, and oxalate in that order.

Discovery of ion-adsorption type deposits of rare earth elements (REE) in Southwest Japan with speciation of REE by extended X-ray absorption fine structure spectroscopy

Discovery of ion-adsorption type deposits of rare earth elements (REE) in Southwest Japan with speciation of REE by extended X-ray absorption fine structure spectroscopy

Distribution and speciation of rare earth elements in coal combustion by-products via synchrotron microscopy and spectroscopy

Rare earth element (REE) binding environments and associated mineral phases in coal and coal combustion byproducts (CCBs) are not well understood. Advanced characterization of REEs' binding environments before, during, and after production can be vital in establishing an economically viable recovery method for REEs from these materials. This study characterized different REE distributions, cerium (Ce) oxidation states, and Ce binding environments in 11 CCBs collected from various locales via X-ray fluorescence (XRF) elemental mapping and X-ray absorption near edge structure (XANES) at Stanford Synchrotron Radiation Lightsource (SSRL). Bulk Ce LIII edge XANES identified Ce(III) (>85%) as the predominant Ce oxidation state in all studied samples. Ce speciation and XRF elemental map analyses further reveal the REEs in studied samples can be (1) dispersed throughout the aluminosilicate glass phase, (2) as micro-particles in large glass grain, or (3) as independent trace phases in studied samples. Both fly ash and bottom ash contain mainly Ce(III) micro-hotspots (<40 μm), co-localization with a range of elements, including, but not limited to: P, S, Ca, Ti, and Mn. At microscale, Ce can change from Ce(III) to mixture of Ce(III) and Ce(IV) and to 100% Ce(IV) oxide, revealing potential REE-phase decomposition and oxidation in coal and coal combustion process. Our study also observed intraparticle and interparticle distribution difference between light REEs and heavy REEs. The synchrotron-based characterization confirmed the presence of these trace, previously only theorized, phases during the combustion process and ultimately may inform the simplification of separation and extraction processes for REE from different CCBs.

Experimental evidence of REE size fraction redistribution during redox variation in wetland soil

The evolution of rare earth element (REE) speciation between reducing and oxidizing conditions in a riparian wetland soil was studied relative to the size fractionation of the solution. In all size fractions obtained from the reduced and oxidized soil solutions, the following analyses were carried out: organic matter (OM) characterization, transmission electron microscopy (TEM) observations as well as major and trace element analyses. Significant REE redistribution and speciation evolution between the various size fractions were observed. Under reducing conditions, the REEs were bound to colloidal and dissolved OM (<2μm size fractions). By contrast, under oxidizing conditions, they were distributed in particulate (>2μm size fraction), colloidal (<2μm size fraction), organic and Fe-enriched fractions. In the particulate size fraction, the REEs were bound to humic and bacterial OM embedding Fe nano-oxides. The resulting REE pattern showed a strong enrichment in heavy REEs (HREEs) in response to REE binding to specific bacterial OM functional groups. In the largest colloidal size fraction (0.2μm–30kDa), the REEs were bound to humic substances (HS). The lowest colloidal size fraction (<30kDa) is poorly concentrated in the REEs and the REE pattern showed an increase in the middle REEs (MREEs) and heavy REEs (HREEs) corresponding to a low REE loading on HS. A comparison of the REE patterns in the present experimental and field measurements demonstrated that, in riparian wetlands, under a high-water level, reducing conditions are insufficient to allow for the dissolution of the entire Fe nano-oxide pool formed during the oxidative period. Therefore, even under reducing conditions, Fe(III) seems to remain a potential scavenger of REEs.

Rare Earth Elements in Mineral Deposits: Speciation in Hydrothermal Fluids and Partitioning in Calcite

Studying the speciation and mineral-fluid partitioning of the rare earth elements (REE) allows us to delineate the key processes responsible for the formation of economic REE mineral deposits in natural systems. Hydrothermal REE-bearing calcite is typically hosted in carbonatites and alkaline rocks, such as the giant Bayan Obo REE deposit in China and potential REE deposits such as Bear Lodge, WY. The compositions of these hydrothermal veins yield valuable information regarding pressure (P), temperature (T), salinity, and other physicochemical conditions under which the REE can be fractionated and concentrated in crustal fluids. This study presents numerical simulation results of the speciation of REE in aqueous NaCl-H2O-CO2-bearing hydrothermal fluids and a new partitioning model between calcite and fluids at different P-T-x conditions. Results show that, in a high CO2 and low salinity system, bicarbonate/carbonate are the main transporting ligands for the REE, but predominance shifts to chloride complexes in systems with high CO2 and high salinity. Hydroxyl REE complexes may be important for the solubility and transport of the REE in alkaline fluids. These numerical predictions allow us to make quantitative interpretations of hydrothermal processes in REE mineral deposits, particularly in carbonatites, and show where future experimental work will be essential in improving our modeling capabilities for these ore-forming processes.

Rare earth elements sorption to iron oxyhydroxide: Model development and application to groundwater

Iron oxyhydroxides are among the most important colloids that control rare earth elements (REE) concentrations and transport in natural hydrosystems. In this study, REE surface complexation to iron oxyhydroxides (Fe(OH)3(a)) was described by using the Donnan diffuse layer model and a two-site (i.e. ≡FesOH and ≡FewOH) model. The specific surface area and pH of zero charge were fixed as 100000 m2/mol and 8.0, respectively. The surface site density for weak and strong binding sites were fixed at 0.1 moL/mol Fe (≡FewOH) and 0.001 moL/mol Fe (≡FesOH) respectively. The two site types were used with pKa1int = 7.29 and pKa2int = 8.93. Using linear free energy relationship, the estimated equilibrium surface complexation constants (log K) increased from light REE (LREE) to heavy REE (HREE). Results of REE modeling calculation using the determined log K revealed a good fit of experimental data, showing an order of sorption on iron oxyhydroxides: HREE > MREE > LREE and preferential sorption of HREE at a lower pH. However, sorption edges only showed a slight change with ionic strength (0.1–0.7 moL/L) for the whole REE series. The generalized model was subsequently used to evaluate the impact of iron oxyhydroxides on REE speciation in groundwater. Application of the model to “model groundwater” showed that iron oxyhydroxide complexes of REE were significant in near neutral and weakly alkaline pH. This study contributes to putting forward a comprehensive database which would be useful for the application of surface complexation model to describe REE sorption by amorphous ferric hydroxides in nature.

Petrographic and geochemical features of the dolostones at the Gölboğazı Formation (Upper Devonian), Southwest Konya, Turkey

This paper describes the occurrence of dolostone and the mechanism of dolomitization of the Upper Devonian Golbogazi Formation in the allochthonous Taurus Mountains Aladag unit in Turkey. The Upper Devonian Golbogazi Formation carbonates, with dominant ostracod-bearing mudstone and wackestone, formed tidal and subtidal environments, and some of these rocks were dolomitized from shallow to deep burial. On the basis of the field, the petrographic and geochemical features, four different replaceable and cement dolostone phases have been recognized. The replacive dolostones contain (1) very fine to fine crystalline planar-s dolostone (df1), (2) medium to coarse crystalline planar-s to planar-e dolostone (df2), (3) coarse to very coarse crystalline non-planar-a dolostone (df3), and (4) coarse to very coarse crystalline planar dolostone cement (df4). The replacive dolostones are disordered to moderate the ordered and calcium-rich. They are non-stoichiometric and have 46–59 mol% CaCO3 and 41–54 mol% MgCO3 total contents. The df1 dolostones have MgCO3 contents of 41–54 mol%, the df2 dolostones have 41–53 mol%, the df3 dolostones have 49 mol%, and the df4 dolostones have 49–50 mol%, respectively. The Golbogazi dolostones have δ18O values of −9.44 to −2.20‰ Vienna Pee Dee Belemnite (VPDB) and δ13C values of −1.58 to +2.52 VPDB. Sr, Na, Mn, and Fe concentrations of replacive dolostones are 74–184, 148–593, below detection level (bdl)–619, and 1049–9233 ppm, respectively. The petrographic and geochemical data demonstrate that the replacive dolostones occurred prior to the chemical compaction at shallow to intermediate burial depths from Late Devonian seawater and/or seawater lightly modified by water–rock interaction process and later recrystallized by basinal brines at increasing burial depths and temperature. The North American Shale Composite-normalized rare earth element values of both limestone and dolostone show very similar rare earth element patterns characterized by slightly or considerably negative cerium (Ce) anomalies and a clear depletion in all rare earth element species. The dedolomitization observed in the Golbogazi Formation is thought to occur by the oxidizing effect of the meteoric water in the shallow burial environment during the telodiagenesis.