Fractionation Of Rare Earth Elements Research Articles

A study on speciation and enrichment of rare earth elements (REE) by sequential extraction from a potential coal fly ash resource and its role in REE extractability

Coal fly ash (CFA) is a potential secondary Rare Earth Element (REE) source that needs an efficient enrichment and extraction process. Annually, coal-fired power plants generate nearly 1 billion tonnes of coal ash. India alone produced 270.82 million tonnes of CFA in 2021–22. The average global concentration of REE in coal ash is 403.5 mg/kg. The present authors have already studied some promising CFAs from Indian thermal power stations and one such CFA is used in the present study for the sequential extraction (SE), speciation, and enrichment of REEs. Organic acids are used for SE to determine different fractions of REEs and it is found that REEs are mostly associated with amorphous Mn-oxide and organic and sulfide fractions. About 84% of REEs are in the glassy phase that SE cannot dissolve. The main components of CFA and SE residues are quartz, mullite, and glassy phase (52.0–59.2%). The XRF analysis showed that CFA is ‘Class F' (ASTM C618–19). The ESEM – EDS and backscatter imaging revealed monazite-(La) mineral as the REE carrier in CFA. Furthermore, enrichment studies using acid and alkali media have been performed. Alkali treatment with NaOH and KOH increased total REE by 1.61 and 1.32 times, respectively. Acidic treatment with HCl and oxalic acid increased total REE by 1.27 and 1.09 times, respectively. Therefore, NaOH followed by HCl treatment could be a cost-effective and sustainable REE enrichment and extraction method from CFA.

Concentration, speciation, and fractionation of rare earth elements in alluvial soils in contiguous karst landform, southwestern China

Karst is a unique landform formed by strong chemical weathering of carbonate rocks. This study investigated the concentration and speciation of rare earth elements and yttrium (REY) in alluvial soils and REY fractionation from carbonate rocks and alluvial soils in the world's largest contiguous karst landform in southwestern China. The results showed that the REY of alluvial soils ranged from 73.77 to 1251.56 μg⋅g−1, with a median value of 230.30 μg⋅g−1, which was higher than that of alluvial soils across China (178 μg⋅g−1) and the upper continental crust (168 μg⋅g−1), revealing a high background of REY in these karst areas. Meanwhile, the average REY in alluvial soils (244.96 μg⋅g−1) was close to 14 times that in carbonate rocks (17.61 μg⋅g−1) in the study area, indicating that REY was significantly enriched in the pedogenesis. Correlation analysis showed that the REY concentration was not significantly related to any single factor (i.e., Fe2O3, MnO, Al2O3, TOC, pH, or CIX). BCR speciation analysis revealed a declining trend in the proportion of REY across the residual (F4, 73.21 %), reducible (F2, 19.40 %), oxidizable (F3, 6.89 %), and weakly acid-extracted (F1, 0.50 %) phases. Additionally, significant REY fractionations from carbonate rocks to alluvial soils were observed. The bedrock-normalized REY pattern revealed an enrichment of light rare-earth elements (LREE) and middle rare-earth elements (MREE), a depletion of heavy rare-earth elements and yttrium (HREY), and positive Ce and Gd anomalies. Secondary mineral phases that formed during weathering—such as clay minerals, oxyhydroxides, phosphates, and organic matter—played an important role in the retention and fractionation of the REY in the soils. Besides these natural factors, anthropogenic inputs also contributed to the REY fractionation, as indicated by the slight positive Gd anomaly in the karst alluvial soils. Furthermore, the differences of δCe and δEu in the soils developed from three types of pedogenic rocks—including carbonate, basalt, and granite—were discussed. The different δEu anomalies could help to identify the parent rocks of alluvial soils.

U-Pb Geochronology, Geochemistry and Geological Significance of the Yongfeng Composite Granitic Pluton in Southern Jiangxi Province

The Yongfeng composite granitic pluton, located in the southern section of the Nanling area, is composed of the Yongfeng and Longshi biotite monzonitic granites. In order to reveal the genesis of this composite granitic pluton and its relationship with mineralization, this study conducted zircon U-Pb dating, whole-rock major and trace element analysis, and biotite electron probe analysis. The results show that the Yongfeng composite granitic pluton is rich in silicon and alkali, weakly peraluminous, and poor in calcium and iron. It shows the enrichment of light rare earth elements and a significant fractionation of light and heavy rare earth elements. It also shows the enrichment of large ion lithophile elements and depletion of Ba, K, P, Eu, and Ti relative to the primitive mantle. The contents of TFe2O3, MgO, CaO, TiO2, and P2O5 are low and decrease with increasing SiO2 content. The Yongfeng composite granitic pluton does not contain alkaline dark minerals. Its average zircon saturation temperature is 776 °C, average TFe2O3/MgO is 4.81, and average Zr + Nb + Ce + Y is 280.6 ppm, which correspond to a highly fractionated I-type granite. The Yongfeng and Longshi granites were respectively formed at 152.0 ± 1.0 Ma–151.3 ± 1.1 Ma and 148.9 ± 1.2 Ma. They were formed in the extensional tectonic setting during the post-orogenic stage, under the control of the breakup or retreat of the backplate after the subduction of the Pacific Plate into the Nanling hinterland. The magmatic system of the Yongfeng composite granitic pluton is characterized by high fractionation, high content of F, high temperature, and low oxygen fugacity, which is conducive to mineralization of Sn, Mo, and fluorite.

Optimized thermodynamic properties of REE aqueous species (REE3+ and REEOH2+) and experimental database for modeling the solubility of REE phosphate minerals (monazite, xenotime, and rhabdophane) from 25 to 300 °C

Rare earth elements (REE) are critical elements found in monazite, xenotime, and hydrated REE phosphates which typically form in hydrothermal mineral deposits. Accurate predictions of the solubility of these REE phosphates and the speciation of REE in aqueous fluids are both key to understanding the controls on the transport, fractionation, and deposition of REE in natural systems. Previous monazite and xenotime solubility experiments indicate the presence of large discrepancies between experimentally derived solubility constants versus calculated solubilities by combining different data sources for the thermodynamic properties of minerals and aqueous species at hydrothermal conditions. In this study, these discrepancies were resolved by using the program GEMSFITS to optimize the standard partial molal Gibbs energy of formation (ΔfG°298) of REE aqueous species (REE3+ and REE hydroxyl complexes) at 298.15 K and 1 bar while keeping the thermodynamic properties fixed for the REE phosphates. A comprehensive experimental database was compiled using solubility data available between 25 and 300 °C. The latter permits conducting thermodynamic parameter optimization of ΔfG°298 for REE aqueous species. Optimal matching of the rhabdophane solubility data between 25 and 100 °C requires modifying the ΔfG°298 values of REE3+ by 1–6 kJ/mol, whereas matching of the monazite solubility data between 100 and 300 °C requires modifying the ΔfG°298 values of both REE3+ and REEOH2+ by ~15–31 kJ/mol and ~ 2–10 kJ/mol, respectively. For xenotime, adjustments of ΔfG°298 values by 1–26 kJ/mol are only necessary for the REE3+ species. The optimizations indicate that the solubility of monazite in acidic solutions is controlled by the light (L)REE3+ species at <150 °C and the LREEOH2+ species at >150 °C, whereas the solubility of xenotime is controlled by the heavy (H)REE3+ species between 25 and 300 °C. Based on the optimization results, we conclude that the revised Helgeson-Kirkham-Flowers equation of state does not reliably predict the thermodynamic properties of REE3+, REEOH2+, and likely other REE hydroxyl species at hydrothermal conditions. We therefore provide an experimental database (ThermoExp_REE) as a basic framework for future updates, extensions with other ligands, and optimizations as new experimental REE data become available. The optimized thermodynamic properties of aqueous species and minerals are available open access to accurately predict the solubility of REE phosphates in fluid-rock systems.

Pre-concentration and partial fractionation of rare earth elements by ion exchange

This work evaluated the pre-concentration and fractionation of rare earth elements (REE) from an acid mine drainage (AMD), by using ion exchange technique. The AMD presents pH 3.50, total REE content of approximately 45.5 mg g−1, 1.3 g L−1 of sulfate and 253 mg L−1 of Ca, Al, Mg as the main impurities. The tests were carried out in columns using a commercial strongly acidic cation exchange resin, LEWATIT® MDS 200H. Regarding the loading step, the resin proved to be more selective for La, Ce, Pr and Nd. A total loading capacity of 0.25 mmol g−1 was obtained for the REE and 2.64 mmol g−1 for the impurities, with efficiencies of 78% and 48%, respectively. Regarding fractionation, the 0.01 mol L−1 NH4EDTA promotes the best elution profiles with more narrow and separated bands. Elution efficiency was greater for the heavy REE, near 100% and only 40% for the light ones. Aluminum and Ca were eluted with an efficiency of approx. 3%. Aluminum was the most difficult impurity to separate from REE.

Fractionation of rare earth elements in soil profiles along an elevation gradient in central Taiwan

The distribution of rare earth elements (REEs) in soils is affected by climate, which is one of the main factors controlling soil formation. However, variations in the geochemical behavior of soil REEs with pedoclimatic changes have rarely been investigated. This study determined the mobilization/retention and fractionation of REEs in nine soil profiles derived from sandy shale along an elevation gradient from 49 m to 2394 m above sea level in the Central Mountain Range of Taiwan. The experimental results indicated a gradually decreased ΣREEs trend with increasing elevation/rainfall. Clay content significantly (p < 0.05) correlated with REEs, which accumulated in argillic horizons. Moreover, a decreasing GdN/YbN ratio with increasing secondary minerals (i.e., clay and pedogenic Fe and Al oxides) implied their preferential sequestration tendency for heavy REEs over light REEs. This preferential association coupled with intensifying illuviation along the climatic gradient, resulted in increasing LaN/SmN and decreasing GdN/YbN ratios with increasing weathering degree and elevation (p < 0.01). Our results demonstrate that in the studied humid tropical region, increasing moisture availability caused by higher rainfall and lower air temperatures with rising elevation has led to stronger illuviation and more advanced soil development, which is reflected in REE fractionation and can be quantified by the ratios GdN/YbN and LaN/SmN.

Ocean–Continent Conversion in Beishan Orogenic Belt: Evidence from Geochemical and Zircon U-Pb-Hf Isotopic Data of Luotuoquan A-Type Granite

Devonian magmatism is one of the most important tectonothermal events in the Central Asian Orogenic Belt (CAOB). However, little is known regarding the petrogenesis and geodynamic setting of the widely distributed Devonian granitoids in the eastern Southern Beishan Orogenic Belt (SBOB). Early-Devonian granitic magmatism has been recognized from the Luotuoquan area, and the granites were emplaced between 404.9 Ma and 399.4 Ma according to LA-ICPMS zircon U–Pb dating. Geochemically, the granites exhibit high SiO2 and Al2O3 contents and are enriched in light rare earth elements as well as Rb, Th, Nd, Zr, and Hf, while being depleted in heavy rare earth elements and Ba, U, Sr, and Ti, with distinct rare earth element fractionation and pronounced negative Eu anomalies. According to the comprehensive analysis, they closely resemble the features typically associated with A-type granites. The zircons εHf(t) values are within the range of +0.90–+5.19 (averaged 3.23) for the monzogranite and syenogranite, whereas their TDM2 values fall between 1.05 and 1.34 Ga, suggesting that the magma source of the monzogranite–syenogranite originated from the partial melting of the Mesoproterozoic crust dominated by metagreywackes. Furthermore, the monzogranite and syenogranite exhibit high temperatures (average 782 °C), thin crustal thickness (average 30 km), and A-type characteristics, suggesting their formation in post-collision extensional settings. We propose the closure of the Beishan Ocean occurred before the early Devonian, followed by a transition in the Southern Beishan Orogenic Belt from a compressional to an extensional setting.

U–Pb Dating of Fibrous Dolomite in the Hydrothermal Dolostone of the Dengying Formation, Central Sichuan Basin, and Its Response to Supercontinent Breakup

Super-deep drilling in the central Sichuan Basin encountered volcanic rocks of the Suxiong Formation, which are overlain by multiple hydrothermal alterations within the upper section of the Ediacaran Dengying Formation. This provides an excellent research opportunity to understand the pre-Cambrian hydrothermal activity and geological evolution of the western margin of the Yangtze Craton. Observations revealed the development of a series of hydrothermal dolomite aggregates characterized by the presence of brown sphalerite within fractures and pores of the carbonate rock. Microscopically, the dolomite exhibited fibrous columnar crystallization, forming radial bands with a gradual decrease in crystallization intensity from the center to the periphery. Cathodoluminescence analysis revealed the presence of approximately eight dolomite bands within the aggregate. U–Pb dating from the inner to outer bands yielded isotopic ages of 781 ± 12 Ma for the second band, 683 ± 12 Ma for the fifth, 562 ± 12 Ma for the sixth, and 545.4 ± 6.9 Ma for the seventh. The in situ rare earth element (REE) distribution patterns of the 781 and 683 Ma dolomite bands exhibited similarities. They both showed low total REE content (∑REE), with significant fractionation between light and heavy REEs. Additionally, they exhibited negative anomalies in cerium (Ce) and europium (Eu), while heavy REEs were relatively enriched. The dolomite bands at 562 and 545 Ma also exhibited similar REE characteristics, with low ∑REE and weak fractionation between light and heavy REEs. They also displayed distinct negative anomalies in Ce and Eu, indicating similar distribution patterns. These findings suggested that formation of the banded hydrothermal dolostone occurred during different tectonic events, and the presence of heavy REE-enriched hydrothermal fluids suggested a deep-seated origin. This study has provided preliminary evidence that the Dengying Formation, previously considered to be of the Ediacaran age, has undergone multiple episodes of deep-seated fluid infiltration and alteration since the Mesoproterozoic Era. Importantly, these events coincide with the rifting of the Rodinia and Pannotia supercontinents, aligning with their respective timeframes. This finding raises questions regarding the stratigraphic division and correlation of the formations in the deeply buried core area of the basin.

The translocation and fractionation of rare earth elements (REEs) via the phloem in Phytolacca americana L.

Rare earth elements (REEs) are considered to be emerging contaminants due to their widespread use and lack of recycling. Phytolacca americana L. has great potential for REEs phytoextraction. Our understanding of REEs in P. americana focuses mostly on root absorption and xylem translocation, but the role of phloem translocation has received little attention. In this research, the translocation and fractionation of REEs from phloem to organs in P. americana were investigated. In addition, the effect of organic acids in the REEs translocation via phloem exudates was also examined. The results showed that REEs could transport bidirectionally via the phloem, and 86% of REEs exported from old leaves could move downwards to the root, whereas only 14% of them transported upwards to the young leaves. Heavy rare earth elements (HREEs) enrichment was found in the REEs fractionation processes both from phloem to leaf and from stem to root, indicating that HREEs were preferentially transferred not only down to roots, but also up to the young leaves. The concentration of oxalic acid in phloem exudates was much higher than other organic acids. 94.7% oxalic acid in phloem exudates was preferred to combine with REEs, especially HREEs. Additionally, the concentrations of HREEs had a high positive correlation with oxalic acid in phloem exudates, which demonstrated oxalic acid may play a significant role in the long-distance transport of HREEs in phloem. In conclusion, HREEs have higher translocation ability than light rare earth elements (LREEs) in both xylem and phloem of P. americana. As far as we know, this is the first report focused on the phloem translocation and redistribution of REEs in P. americana, which provides a valuable understanding of the mechanism for phytoremediation of REEs contaminated soils.

Geochemical behavior and source analysis of rare earth elements in intensive agriculture soils through high-resolution sampling

Rare Earth Elements (REEs) are crucial for a low-carbon economy but overuse pollutes ecosystems. Studying their behavior and source in agricultural soils provides vital insights for soil management. To address this, we collected an extensive dataset comprising 2901 topsoil and 733 subsoil samples from an agriculturally dominant region in eastern China, characterized by uniform parent material. This comprehensive dataset enabled a thorough examination of the geochemical behavior and sources of REEs in the region. Our findings revealed the feasibility of utilizing La, Ce, and Y to predict ΣREE, LREE, HREE, and LREE/HREE ratios, thereby enhancing the REEs database for eastern China. The average ΣREE concentration in the study area measured 193.0 μg/g, with LREEs constituting 89 % of this total, representing a slight enrichment relative to the Upper Continental Crust. Notably, the electron-donating ability of Ce exhibited a correlation with Mn, indicating its potential as an indicator of redox reactions. The results obtained through structural equation modeling and random forest analysis identified Al, Ti, and K as the most influential environmental factors affecting ΣREE concentrations. Additionally, the indirect impact of K on ΣREE through pH was established. The strong correlation observed between major elements and Heavy Rare Earth Elements (HREEs) shed light on the mechanisms responsible for the notable fractionation of REEs in topsoil. Furthermore, our investigation underscored the substantial influence of pedogenetic processes on the enrichment and leaching of REEs. Source analysis pinpointed significant contributors to REEs, including fertilizers, pesticides, domestic wastewater, coal fly ash, and the native soil parent material. In conclusion, our study emphasizes the pressing need for judicious control of anthropogenic REE inputs. This step is pivotal not only for ensuring the sustainable utilization of soil but also for ultimately safeguarding ecosystems and environmental quality.

Evolution of weathering products over mylonites of the Lom series at Kissi (Bétaré-Oya Gold District, East-Cameroon): Morphological, mineralogical and geochemical mechanisms for trace and rare earth elements enrichment

Weathering and lateritization processes and their implication to the fractionation of trace and rare earth elements (REEs) in soil materials developed upon mylonites in Kissi area of the Bétaré-Oya Gold District (Lom series, East Cameroon) were assessed through morphological (position on the slopes), mineralogical (X-ray diffraction) and geochemical (X-ray fluorescence and Inductively Coupled Plasma-Mass Spectrometry) investigations. Three (03) representative soil profiles were selected and described according to the topography (upslope, mid-slope and downslope). The resulted weathering products are rich in kaolinite (16–49%), gibbsite (3–17%), goethite (5–10%) and hematite (2–10%), with quartz (30–49%) and muscovite (4–31%) as inherited minerals. Geochemical proxies and related ternary diagrams signal an intense chemical weathering (CIA: 43.3–100%; PIA: 41.9–100%), but weak lateritization (IOL: 11.3–40.8%) of parent mylonite under warm and wet tropical climate, that induce the formation of kaolinitic laterites. These processes are characterized by a weak leaching of SiO2 (79.7–52.2%), but strong one of labile elements (WIP: 48.7 to 0.8%; TRB: 228.9 to 15.1 mg kg−1). Al2O3 (16.2–22.8%) and Fe2O3 (4.2–14.0%) are the slightly enriched major oxides in the weathered materials. Some trace elements including Sc, V, Cr, Co, Ni, Cu, Ga, As, Li, Y, Mo, Cs, Hf, W, Pb, Th, Tl, U, Zr and REEs are reported as strongly enriched compared to mylonite, but weak mineralized according to their average contents in the earth's crust (Maximum Enrichment factor: 1.1–38.8). This gives rise of low mining potential of the current weathering products. Nevertheless, Ce (37.8–453.6 ppm), Ba (34.2–379.6 ppm), Cr (100.0–270.0 ppm), V (108.9–215.0 ppm), Zn (23.4–192.0 ppm), Ni (29.3–170.0 ppm) and Rb (2.5–140.0 ppm) are the most abundant in the soil profiles. Topographically, trace and REEs are preferentially enriched and mineralized at mid-slope and downslope of the interfluve. But, the overall behavior and enrichment of elements in Kissi are controlled by the dissolution of rock-forming minerals and their release in the residual soil system, their incorporation into the crystalline structure of newly formed secondary minerals and the lateral water runoff along the slope gradient.

Insights from distribution and fractionation of the rare earth elements into As enrichment in the Singe Tsangpo River Basin

The geogenic As enrichment occurs extensively in the major river basin from the Tibetan Plateau, while the knowledge involved with the underlying mechanisms is far from completion. The present study utilized the geochemical behaviors of rare earth elements (REE) to study the hydrogeochemical evolution and As enrichment in the Singe Tsnagpo River basin, a typical As-rich river basin in the Tibetan Plateau. The river water was characterized by significant positive Eu anomalies and slight negative Ce anomalies, indicating the hydrogeochemical control of oxidative weathering of sourcing rocks and the contribution of felsic rocks. The PHREEQC modeling results suggested that the carbonate weathering contributed to the complexation of REE in the river water, where REE(CO3)+ and REE(CO3)2− were the predominant complex species. Besides, the reversing scenarios of HREE/LREE enrichment in the river water/sediments suggested a critical control of iron (hydr)oxides on the REE fractionation due to the preferential adsorption of LREE compared with HREE. Interestingly, the variations in Y/Ni and Cr/V ratios from the river sediments suggested a different contribution of sourcing rock weathering along the river flow path, where ultramafic rock showed a substantial contribution to the river sediments in the lower reaches and granite source is predominant in the upper reaches. It was also notable that the concurrent enrichment of REE and As in the river waters showed a response to the substantial enhancement of chemical weathering in the upper reaches of the STR basin, which was evidenced by the corresponding increases in the electrical conductivity and the δ18O values in the river waters. The present study thus provides new insights into utilizing REE as environmental tracers for studying hydrogeochemical evolution and As enrichment in the STR basin, which could also apply to similar alpine arid and cold river basins.

Accumulation, translocation, and fractionation of rare earth elements (REEs) in fern species of hyperaccumulators and non-hyperaccumulators growing in urban areas

The issue of ion-adsorption type rare earth deposits (IADs) in urban areas of South China has garnered significant attention due to its environmental implications. Hyperaccumulator-based phytoremediation is a potentially effective solution for reducing the environmental impact of IADs in urban areas, particularly using ferns as they are known to be REE hyperaccumulators. However, the ability of different fern species to accumulate REEs in urban areas remains unknown. In this study, four fern species, including known hyperaccumulators (Dicranopteris linearis and Blechnum orientale) and other ferns (Pteris ensiformis and Cibotium barometz), were studied to investigate their REE accumulation abilities in the Guangzhou urban area. The aboveground parts of Dicranopteris linearis (848.7 μg g−1) and Blechum orientale (1046.8 μg g−1) have been found to accumulate high concentrations of REEs, demonstrating they probably can be applied for phytoremediation in the natural environments. Despite having lower REE concentrations than REE hyperaccumulators, Pteris ensiformis and Cibotium barometz still probably have the function as phytostabilizers in urban areas, as REEs can be enriched in their roots beyond the normal levels of plants. The enrichment of REEs in ferns is influenced by the availability of various nutrients (K, Ca, Fe, and P), which probably can be associated with different growth processes. The four fern species show LREE enrichment, moderate Eu anomalies and different Ce anomalies. It is difficult to absorb and transfer Ce to the aboveground parts of Blechnum orientale and Cibotium barometz. The study also identified selective enrichment of Ce in Pteris ensiformis, which has potential for comprehensive extraction of REEs when combined with other REE hyperaccumulators. REE fractionations are probably determined by the specific characteristics of different fern parts. Overall, these findings provide insights for addressing potential environmental problems related to IADs and offer guidelines for phytoremediation technology in addressing high REE levels in urban areas.

Agricultural activity on the Mun River basin: insight from spatial distribution and sources of dissolved rare earth elements in northeast Thailand.

Rare earth elements (REE) are emerging pollutants of concern, impacted by intensive fertilizer use and discharge of human and animal waste into agricultural watersheds. However, the natural values and potential anthropogenic enrichment of REE in aqueous systems of the agricultural basins remain poorly understood. This study investigated the spatial variation of dissolved REE in a predominantly agricultural river (Mun River) in northeast Thailand. Dissolved ΣREE concentrations in the Mun River ranged from 5.08 to 272.91 ng/L, with the highest concentrations observed in the middle reaches where agricultural fertilizers and wastewater increased dissolved REE concentrations. The PAAS-normalized patterns and dissolved Eu anomaly jointly reveal that the dissolved ΣREE mainly originated from local rocks and agricultural fertilizers. The dissolved REE in the Mun River is characteristic of a depleted light REE relative to heavy REE, slightly negative Ce anomaly, positive Eu anomaly, and positive Gd anomaly in a punctate distribution. The correlation analysis of (La/Yb)N with fluvial pH and HCO3- indicates that the water environment characteristics of the Mun River control dissolved REE fractionation. The Ce anomaly is associated with the oxidation environment, whereas the Eu anomaly is linked to the lithologic inheritance. Positive punctate Gd anomalies are influenced by human-caused wastewater discharge and applying fertilizers, raising Gd concentrations beyond natural background levels. This study has suggested that the geochemical characteristics of dissolved REE are affected by agricultural disturbances, and future environmental research on dissolved REE is essential to clarifying the impacts of REE on agriculture, the environment, and human health.

Experimental alteration of allanite at 200°C: the role of pH and aqueous ligands

Abstract Allanite is a major host of rare earth elements (REEs) in the continental crust. In this study, reaction mechanisms behind allanite alteration are investigated through batch experiment runs on natural allanite grains in carbonate-bearing hydrothermal fluids at 200°C, with initial acidic (pH = 4) or alkaline (pH = 8) conditions and with different aqueous ligands (120 mmol kg −1 of F, Cl, P or S). Time-series experiment runs in F-doped systems at different durations between 15 and 180 days reached a steady state at 120 days. The pH efficiently controls the allanite alteration process, with initial high pH, alkaline conditions being more reactive (75% alteration compared with 25% under acidic conditions). The ligand also significantly influences the alteration process under initial acidic conditions with the P-doped system (70%) almost non-reactive for the Cl- and S-doped systems (&lt;5%). In the alteration rim, REEs are mainly redistributed in REE-bearing phases either as carbonates (F-doped) or phosphates (P-doped). The relatively flat REE-normalized patterns of the recovered experimental fluids suggest a fractionation of light rare earth elements (LREEs) over heavy rare earth elements (HREEs) during the course of the alteration reactions. It is proposed that secondary REE mineral precipitation at the reaction front creates a local disequilibrium in the solution and a steep chemical gradient promoting allanite dissolution and thus its alterability.

Geochemical characteristics and migration patterns of rare earth elements in coal mining subsidence lakes under the influence of multiple factors

Mining activities cause surface subsidence and the formation of subsidence lakes, which dynamically change with the continuous coal mining activities. Under the combined influence of various human activities such as agriculture, aquaculture, and floating photovoltaic (FPV), the lake environment undergoes continuous changes, thereby altering the geochemical characteristics of rare earth elements (REEs) in the sediment. This study focused on the subsidence lakes in the Huainan coalfield in eastern China to examine the REEs content in the sediment, elucidated the temporal variations and geochemical characteristics of REEs distribution, explored the main controlling factors of REEs in the sediment, and revealed the migration and transformation behavior of REEs during dynamic subsidence processes. The study revealed that the migration pattern of REEs in the sediment was closely related to the duration of subsidence. The average content of REEs in lake sediments with subsidence duration <5 years increased from 219 μg·g−1 to 248 μg·g−1 compared to the soil, showing an enrichment model primarily driven by rainwater runoff, groundwater input retention, and mineral dissolution. With further subsidence, the processes of reduction dissolution of Fe–Mn oxides/hydroxides, organic colloid adsorption, and hydraulic disturbance gradually replaced the aforementioned enrichment behavior as the main migration pathways, resulting in a decrease in the average REEs content in the sediment to 179 μg·g−1 for subsidence durations exceeding 10 years. There was no strong correlation between REEs fractionation and subsidence duration. Artificial activities, such as FPV, are important factors causing Cerium and Erbium anomalies in some subsidence lake sediments. This study was not only of significant importance for understanding the migration, distribution, and environmental behavior of pollutants in aquatic environments under the interference of human activities but also provided a solid theoretical foundation for the future management of coal mining subsidence lakes.

The use of rare earth element profiles as a proxy for a fractionation source and mine-waste provenance

Rare earth elements (REEs) have been determined in acid mine drainage samples from the Wiśniówka area, south-central Poland. Two benchmark acid pit ponds, i.e., Podwiśniówka (PwIIb) and Wiśniówka Duża (WD), have shown diverse contents of sulfates, phosphates, REEs and metal(loid)s. Moreover, these ponds exhibit different NASC-normalized REE concentration patterns: (i) a positive middle REE anomaly in PwIIb and (ii) a positive heavy REE anomaly in WD, regardless of sampling time. This MREE anomaly has also been highlighted in a small tailings pile pool showing high contents of metal(loid)s, including As (3.86 g/L) and REEs (90.1 mg/L). In contrast, the light REE (LaEu)-rich profiles are recorded in all Upper Cambrian rock series of the study area. However, the Pw geologic section is distinctly enriched in pyrite, goethite/hematite and carbonaceous clayey-silty shales compared to its WD counterpart that contains a lesser amount of these components, but many more quartzite/sandstone beds. The Pw mineral-lithologic pattern favors selective partitioning of heavy REEs to abundant Fe- and Al-oxyhydroxides and organic matter. Both very short solute transport from sheer rock faces to pit ponds and a low pH of acid waters (mean of 2.3 to 3.0) indicate that scavenging/adsorption and mineral co-precipitation of REEs in a water column may be negligible. This inference is also backed up by overlapping REE profiles at different depths of acid pit ponds. Taken together, this implies that preferential fractionation of REEs takes place primarily during on-site weathering of pyrite and REE-bearing minerals in different rock media thus leading to changes in the Pw- and WD shale-normalized REE concentration patterns at source. The characteristic Pw roof-shaped (convex-up) profile in water samples has been used as a proxy for tracing the most detrimental Podwiśniówka As-bearing mine-waste that were scattered within the mining area a couple of years ago.

The Behavior of Rare Earth Elements during Green Clay Authigenesis on the Congo Continental Shelf

Clay mineral authigenesis at continental margins plays an important role in global marine element cycles. However, despite being increasingly used as tracers for both modern and past oceanographic conditions, the behavior of the rare earth elements (REEs) and their isotopes during marine clay authigenesis still remains poorly known. In this study, we report on a detailed geochemical investigation of glauconite from the West African continental shelf, near the mouth of the Congo River. Elemental, neodymium, and hafnium isotope analyses were conducted on both acid leachate and separated clay-size fractions of glauconite pellets, in order to investigate the behavior of REE during the formation of authigenic clays. Our data indicate that kaolinite dissolution and subsequent Fe-bearing clay authigenesis act as a net source of REEs to seawater. We show that enhanced glauconitization, as inferred from increasing Fe and K contents, is accompanied by significant decoupling of the REE toward markedly LREE-enriched shale-normalized patterns in neoformed clay separates. Using both Nd and Hf isotopes and SEM observations, we rule out any seawater influence and argue that this shift primarily reflects the progressively overwhelming presence of insoluble nanocrystals of detrital LREE-rich phosphates, which are known to occur in close association with kaolinite in tropical soils. Due to their marked insolubility in surface environments, such nanocrystals can be preserved during kaolinite dissolution and subsequently incorporated into the aggregates of authigenic green clays forming the peloids. Most strikingly, we show that the combined influence of net REE loss (due to kaolinite dissolution) and decoupling (due to subsequent entrapment of inherited LREE-bearing accessory phases into neoformed clay minerals) is accompanied by preferential release of a dissolved REE fraction characterized by seawater-like distribution patterns. These findings reinforce the emerging view that clay mineral dissolution and authigenesis at continental margins possibly play a major role in marine REE cycling.

Bioconcentration and translocation of rare earth elements in plants collected from three legacy mine sites in Portugal

Rare earth elements (REE), a group of emerging contaminants with commercial and technological applications, share many physical and chemical characteristics and have thus been used as accurate tracers of various environmental samples. They have been shown to increase in receiving waters following the dissolution of host-rock material during mining activities. In this study, spontaneous vegetation and related media were collected from three Portuguese legacy mine sites in November 2020 to evaluate the phytoavailability and fate of REE. Water, soil and plant data were analyzed in the context of the 1) prevailing geochemical context, 2) the mining context, and 3) plant effects. This study presents the REE signatures for different plant species and links the signatures to a potential source of bioavailable REE. The REE accumulated in plant tissue seems to reflect the REE signature of surface waters in the mining areas, showing enrichment in middle REE. Although the soils, sediments, and waters in this study had similar features, certain plants seemed better adapted to translocating Light REE and Eu over others. Given that REE are readily available within the field conditions of a mining site, this study shows how plant physiology and biologic preference towards particular REE contribute to the fractionation of REE and create a unique signature dependent on plant type.

Dissolved rare earth elements distribution and fractionation in a subtropical coastal river: a case study from Jiulong River, Southeast China

Dissolved rare earth elements distribution and fractionation in a subtropical coastal river: a case study from Jiulong River, Southeast China