Uptake Of Rare Earth Elements Research Articles

Acute and chronic toxicity of rare earth elements-enriched sediments from a prospective mining area: Effects on life history traits, behavioural and physiological responses of Gammarus fossarum (Crustacea Amphipoda)

Rare earth elements (REE) have an essential role and growing importance in the world's economy. They are attracting interest from society, policymakers, and scientists. The rapidly growing global demand for REE in several strategic industrial and agricultural sectors led many countries to consider the (re)-opening of mining activities for REE extraction. Hence, their increasing use led to the disruption of their biogeochemical cycles with anthropic abnormalities already observed in aquatic ecosystems. Nonetheless, REE remain less studied, and their mechanisms of toxicity actions are not fully understood. As amphipods, Gammarus fossarum represent an important part of the aquatic macroinvertebrate assemblage and are generally used in ecotoxicological studies for their high ecological relevance. However, their use for the study of REE effects has been rather limited so far. The current study aims to assess the potential effects of two naturally REE-enriched sediments (N2 and B4) on G. fossarum. Effects on life history traits, behavioural and physiological responses have been evaluated. Exposing G. fossarum males for 72h to sediments N2 and B4 led to a decrease in haemolymph osmolality and locomotion while an increase in ventilatory activity was observed. Exposing G. fossarum pre-copula pairs with females at the same reproductive stage to the naturally REE-enriched sediments, for one moult cycle duration (∼30 days) showed that sediment B4 led to i) a significant uptake of REE, ii) a significant decrease in the proportion of females with oocytes and iii) a significant reduction in the total number of juveniles. The physicochemical analyses of sediments showed that B4 contains the highest amount of REE with a higher proportion of light REE. The present study gives the first insights into the potential toxicity of REE on G. fossarum as they may have deleterious effects on G. fossarum population's dynamics, which may alter the functioning of aquatic ecosystems.

Rare earth elements sequestration in phytoliths: Partitioning patterns and influencing mechanism

Rare earth elements (REEs) are integral to numerous high-tech industries, yet their biogeochemical cycling within ecosystems remains inadequately characterized. Recently, phytoliths have been identified as potentially significant sinks for REEs; however, their role in the cycling of these elements has been underestimated. In this work, we investigate the accumulation of REEs in phytoliths (PhytREEs) within the Greater Khingan Mountains region, employing an optimized wet oxidation method combined with heavy liquid flotation to quantify PhytREEs contents in surface soils. The results revealed an elevation-dependent pattern of PhytREEs concentration, with heightened levels at higher altitudes and diminishing concentrations towards the eastern plains. The enrichment coefficient of PhytREEs (ECPhytREEs) was found to be approximately 2.7 %, indicative of a moderately selective sequestration process. The multivariate analysis indicated that terrain complexity, climatic patterns, soil texture, and organic matter significantly influence the uptake and storage of REEs in plants, subsequently affecting their partitioning in phytoliths. Among these factors, the complexation of REEs with organic matter emerged as a pivotal mechanism facilitating their immobilization within phytoliths. Soil characteristics also play a non-negligible role in modulating REEs dynamics. Our findings highlight the predominant influence of climate on PhytREE storage, suggesting that climatic variables are the primary drivers modulating the bioavailability and ultimate sequestration of REEs within phytoliths. This study enhances our understanding of the biotic-abiotic interplay in the sequestration of REEs and underscores the need to incorporate phytoliths into models of terrestrial REE cycling.

Facile synthesis of eco-friendly alginate-chitosan bio-adsorbent for critical raw materials adsorption: A comprehensive study

Sustainable management of critical raw materials is of paramount importance to ensure a steady supply and reduce environmental impact. The application of newly synthesized and environmentally friendly ALG@CS material as a bio-adsorbent for the effective rare earth elements removal from aqueous solution has been presented. The synthesized material underwent FTIR, XPS, EDX, and SEM analysis to determine its suitability for metal uptake. To evaluate the adsorption capacity of ALG@CS for rare earth elements several factors were taken into consideration. These factors included alginate:chitosan ratios, bead size, pH level, composite mass, interaction time, metal ion concentration, and temperature, being all varied during the batch mode evaluation process. Under the optimal conditions, the maximum adsorption capacities were found to be 145.90 mg La(III)/g, 168.44 mg Ce(III)/g, 132.51 mg Pr(III)/g, 128.40 mg Nd(III)/g, 154.36 mg Sm(III)/g, and 165.10 mg Ho(III)/g. The equilibrium data fits well with non-linear three-parameter Sips and Redlich-Peterson isotherm models. The PSO model finds the highest process suitability. The synthesized ALG@CS bio-adsorbent showed excellent regenerative capacity in ten cycles, making it a suitable adsorbent for rare earth elements uptake. The unique bio-adsorbents combination allows for efficient critical raw materials adsorption providing a promising solution for their recovery and recycling.

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.

Hyperaccumulator extracts promoting the phytoremediation of rare earth elements (REEs) by Phytolacca americana: Role of active microbial community in rhizosphere hotspots

The increased usage of rare earth elements (REEs) leads to the extensive exploitation of rare earth mines, and the REEs pollution in soil caused by the legacy mine tailings has brought great harm to environment and human health. Although Phytolacca americana can remove REEs from contaminated soil to some extent, there is still an urgent problem to improve its efficiency. Hyperaccumulator extract is a new organic material with potential in metal phytoextraction, but its role in REEs phytoremediation and the related underlying processes remain unclear. In this study, hyperaccumulator extracts from P. americana root (PR), stem (PS), leaf (PL) and EDTA were used to improve the phytoremediation efficiency of REEs with P. americana. Soil zymography was applied to assess the enzyme hotspots’ spatial distribution in the rhizosphere, and the hotspots' microbial communities were also identified. The results indicated that the application of hyperaccumulator extracts improved the biomass and REEs uptake of P. americana, and the highest REEs content in plant was observed in the treatment of PS, which increased 299% compared to that of the control. Hotspots area of β-glucosidase, leucine aminopeptidase and acid phosphatase were concentrated in the pant rhizosphere along the roots and increased 2.2, 5.3 and 2.2 times after PS application compared to unamended soils. The PS application increased the relative abundance of Proteobacteria, Cyanobacteria, Bacteroidota and Firmicutes phyla in rhizosphere. Soil fungi have a higher contribution on promoting REEs activation than that of bacteria. Available P and extractable REEs were leading predictors for the plant biomass and REEs concentrations. The co-occurrence network showed that the application of PS creates a more efficient and stable microbial network compared to other treatments. In conclusion, stem-derived hyperaccumulator extract is excellent in stimulating REEs phytoremediation with P. americana by improving hotspots microbial activities and form a healthy rhizosphere microenvironment.

Regulating Chemisorption and Electrosorption Activity for Efficient Uptake of Rare Earth Elements in Low Concentration on Oxygen-Doped Molybdenum Disulfide.

Recovery of rare earth elements (REEs) with trace amount in environmental applications and nuclear energy is becoming an increasingly urgent issue due to their genotoxicity and important role in society. Here, highly efficient recovery of low-concentration REEs from aqueous solutions by an enhanced chemisorption and electrosorption process of oxygen-doped molybdenum disulfide (O-doped MoS2) electrodes is performed. All REEs could be extremely recovered through a chemisorption and electrosorption coupling (CEC) method, and sorption behaviors were related with their outer-shell electrons. Light, medium, and heavy ((La(III), Gd(III), and Y(III)) rare earth elements were chosen for further investigating the adsorption and recovery performances under low-concentration conditions. Recovery of REEs could approach 100% under a low initial concentration condition where different recovery behaviors occurred with variable chemisorption interactions between REEs and O-doped MoS2. Experimental and theoretical results proved that doping O in MoS2 not only reduced the transfer resistance and improved the electrical double layer thickness of ion storage but also enhanced the chemical interaction of REEs and MoS2. Various outer-shell electrons of REEs performed different surficial chemisorption interactions with exposed sulfur and oxygen atoms of O-doped MoS2. Effects of variants including environmental conditions and operating parameters, such as applied voltage, initial concentration, pH condition, and electrode distance on adsorption capacity and recovery of REEs were examined to optimize the recovery process in order to achieve an ideal selective recovery of REEs. The total desorption of REEs from the O-doped MoS2 electrode was realized within 120 min while the electrode demonstrated a good cycling performance. This work presented a prospective way in establishing a CEC process with a two-dimensional metal sulfide electrode through structure engineering for efficient recovery of REEs within a low concentration range.

Geochemistry of Bled El Hadba phosphorites (NE Algeria): Glauconitization process versus REE-enrichment

Rare earth element (REE) enrichment in Algerian phosphorites has been evoked recently by a number of authors and are considered among the richest Paleocene-Eocene phosphorites worldwide. The Bled El Hadba deposit belongs to the giant Djebel Onk phosphorite complex in northeast Algeria. The deposit was subject to many geological studies that were focused on P2O5 contents for commercial purposes. The upper Thanetian phosphorite layer is about 30 m thick, and subdivided into three sub-layers (lower, main and upper sub-layer), based on P2O5 contents, where the main sub-layer is considered to be the richest. Despite this, few detailed geochemical investigations were carried out on this deposit thus far. In this work, major, trace and REE analyses were conducted on phosphate particles (pellets, coprolites and glauconites) using ‘in situ’ LA-ICP MS, and on whole-rock samples using XRF technique. The results show that the main sub-layer displays the highest whole-rock P2O5 contents, varying between 19.65 and 21.32 wt% compared to the lower (10.47–16.87 wt%) and upper (9.43–13.87 wt%) sub-layers. Among the phosphate particles, glauconites display the lowest P2O5 contents in the three sub-layers (17.45–19.35 wt%) compared to pellets (21.14–24.33 wt%) and coprolites (21.75–24.12 wt%), and largely the highest Al2O3, SiO2, MgO and Fe2O3(t). Glauconites also show higher ΣREE contents (764–2050 ppm) compared to pellets (221–910 ppm) and coprolites (214–909 ppm). Within the glauconite particles, the ΣREE, along with Al2O3, SiO2, MgO, and Fe2O3(t) contents, increase from core to the rim, whereas P2O5 contents decrease, which suggests that glauconitization postdates phosphatization processes. Also, the glauconitization process increase from the lower to the upper sub-layer; this is shown by the positive correlations between Al2O3 contents and those of MgO and SiO2 in one hand, and negative correlations between Al2O3 and P2O5 on the other hand. Ce, Eu, Y anomalies, along with La/Nd ratios and Nd contents, all point towards phosphatization under oxic conditions as a result of warm water upwelling, whereas glauconitization started under more reduced (sub-oxic) conditions; i.e., during early diagenesis, the peak of REE uptake from porewater, and under slow sedimentation rates.Despite their relatively low P2O5 concentrations, the ΣREE contents of the Bled El Hadba phosphate particles record the highest concentrations in all Algerian and north African phosphorites. The main sub-layer is considered to be the most glauconite-rich phosphorite in Algeria. Therefore, more extensive REE analyses are recommended to better evaluate its economic potential in terms of critical raw materials.

Unlocking Strategic and Critical Raw Materials: Assessment of Zinc and REEs Enrichment in Tailings and Zn-Carbonate in a Historical Mining Area (Montevecchio, SW Sardinia)

Mining wastes are often both a potential source of Strategic and Critical Raw Materials (SRMs and CRMs) and a threat to the environment. This study investigated the potential of mining wastes from the Montevecchio district of Sardinia, Italy, as a source of SRMs and CRMs. The tailings from Sanna mine processing plant were characterized by X-ray diffraction, Scanning Electron Microscopy, and Plasma Mass Spectometry, showing contents of 1.2 wt% of lead, 2.6 wt% of zinc, and about 600 mg/kg of Rare Earth Elements (REEs). White patinas formed in the riverbed, composed by Zn-bearing minerals (hydrozincite and zincite), also contain about 2900 mg/kg of REEs. Characterization of white patinas along the Rio Roia Cani evidenced that their precipitation from water also involves an uptake of Rare Earth Elements, enhancing their contents by an order of magnitude compared with tailings. The process of REEs concentration in Zn-bearing minerals of white patinas is a candidate as a tool for the economic recovery of these elements. These findings suggest that mining wastes from the Montevecchio district could be considered a potential resource for extracting SRMs and CRMs.

First assessment of Rare Earth Element organotropism in Solea solea in a coastal area: The West Gironde Mud Patch (France)

Few studies exist on concentration and internal distribution of Rare Earth Elements (REEs) in marine fishes. REEs organotropism was determined in common sole (Solea solea) from the West Gironde Mud Patch (WGMP; N-E Atlantic Coast, France). The highest ∑REEs concentrations occurred in liver (213 ± 49.9 μg kg−1 DW) and gills (119 ± 77.5 μg kg−1 DW) followed by kidneys (57.7 ± 25.5 μg kg−1 DW), whereas the lowest levels were in muscles (4.53 ± 1.36 μg kg−1 DW) of Solea solea. No significant age- or sex-related differences were observed. The organotropism varied among groups of REEs. Light and heavy REEs preferentially accumulated in liver and gills, respectively. All considered organs showed different normalized REEs patterns, suggesting differences in internal distribution processes between organs. Further work should address: (1) baseline levels worldwide, and (2) factors controlling uptake and organ-specific concentration of REEs.

Uptake the rare earth elements Nd, Ce, and La by a commercial diatomite: kinetics, equilibrium, thermodynamic and adsorption mechanism

This study addresses the application and evaluation of diatomite as a low-cost, natural, abundant, and highly efficient adsorbent of Nd3+, Ce3+, and La3+ rare earth elements (REEs). The results revealed that the diatomite was porous and cylindrical, with a specific surface area of 150 m2/g. The diatomite displayed a point of zero charge equal to 1.8, maintaining its surface negatively charged at pH values higher than 1.8, which was beneficial for cationic REEs uptake. At pH 1, all three REEs had their lowest uptake values; at pHs 2–6, the REEs removal efficiency practically did not change. The uptaken percentage increased in the order of La3+ (50%), Ce3+ (77%), and Nd3+ (92%), influenced by the electronegativity of the ions. The Avrami-fractional order (AFO) and Liu isotherm model better fit the kinetic and equilibrium process (qmax = La3+ (22.8 mg g−1), Ce3+ (56.2 mg g−1), and Nd3+ (100.9 mg g−1)). Since the diatomite is highly porous, pore filling/pore-surface diffusion was the main mechanism for REEs adsorption, as well as ion exchange and chelation. The reusability tests revealed that the diatomite could be reused 8 times without losing performance. This research shows that diatomite is an efficient strategy for designing effective, low-cost, sustainable adsorbents to recover REEs from synthetic and real effluents.

The role of root carboxylate release on rare earth element (hyper)accumulation in plants – a biogeochemical perspective on rhizosphere chemistry

AbstractThe paper of van der Ent et al. (Plant Soil 485:247–257, 2023), published in the previous issue, reports the hyperaccumulation of rare earth elements (REE) in plant species from the Proteaceae for the first time. Indeed, the high REE accumulation in Proteaceae is not completely unexpected, given that the plants release large amounts of carboxylates to acquire phosphorus and micronutrients. However, it is somewhat questionable that the efficiency of element mobilization alone sufficiently explains the large variability in REE accumulation among different taxa of Proteaceae or other P-efficient species that typically show low concentrations of REE. Given that REE3+ share chemical similarities to Ca2+ but form stable complexes with ligands similar to Al3+, it is reasonable that uptake and accumulation of REE depend not solely on element mobility but also on the dynamics of element speciation governed by the formation, stability, and fate of carboxylate-REE-complexes in the rhizosheaths. The rationale behind this contention is that for elements with low mobility in soil, changes in chemical speciation may increase the availability only if the complex stabilities that depend on rhizosphere pH allow a breakdown during uptake. In this commentary, we explore the idea that REE accumulation depends on rhizosphere processes related to nutrient acquisition and element exclusion that overlap in time, space, and function depending on the composition of metal-chelating ligands released by plant roots in concert with rhizosphere pH. Based on data from greenhouse and field experiments, we propose a model where plants with a P-mining strategy (hyper)accumulate REE when rhizosphere pH is below a critical value shifting the REE speciation to available forms.

Plasma-Membrane-Localized Transporter NREET1 is Responsible for Rare Earth Element Uptake in Hyperaccumulator Dicranopteris linearis.

Rare earth elements (REEs) are critical for numerous modern technologies, and demand is increasing globally; however, production steps are resource-intensive and environmentally damaging. Some plant species are able to hyperaccumulate REEs, and understanding the biology behind this phenomenon could play a pivotal role in developing more environmentally friendly REE recovery technologies. Here, we identified a REE transporter NRAMP REE Transporter 1 (NREET1) from the REE hyperaccumulator fern Dicranopteris linearis. Although NREET1 belongs to the natural resistance-associated macrophage protein (NRAMP) family, it shares a low similarity with other NRAMP members. When expressed in yeast, NREET1 exhibited REE transport capacity, but it could not transport divalent metals, such as zinc, nickel, manganese, or iron. NREET1 is mainly expressed in D. linearis roots and predominantly localized in the plasma membrane. Expression studies in Arabidopsis thaliana revealed that NREET1 functions as a transporter mediating REE uptake and transfer from root cell walls into the cytoplasm. Moreover, NREET1 has a higher affinity for transporting light REEs compared to heavy REEs, which is consistent to the preferential enrichment of light REEs in field-grown D. linearis. We therefore conclude that NREET1 may play an important role in the uptake and consequently hyperaccumulation of REEs in D. linearis. These findings lay the foundation for the use of synthetic biology techniques to design and produce sustainable, plant-based REE recovery systems.

Rare earth elements in environment and effects on plants: A review scientific paper

Rare earth elements (REEs) are widely distributed in low concentrations in all parts of the biosphere. REEs are not at all rare, their concentration in the earth?s crust is close to 0.015%. REEs include the elements scandium, yttrium and the lanthanides from lanthanum to lutetium. REEs show similar physical and chemical properties. Today REEs are applied in industries and technologies, in agriculture as microfertilizers and feed additives and they are also used in medicine. REEs are dispersed especially as accessory minerals in pegmatites, granites and associated metamorphic volcanic rocks. Out of more than 250 kinds of minerals containing REEs, only bastnaesite and monazite are of economic importance. Their concentration in the soil varies widely and depends on their presence in parental materials, soil texture, organic matter content, pedogenetic processes and anthropogenic activities. REEs are found in small concentrations in surface stagnant and flowing waters as well as in underground waters. They are found in water in both suspended and dissolved form. REEs enter the atmosphere from various sources, largely owing to human activities. The majority of REEs in the atmosphere are carried by microscopic particles. The uptake and consequently accumulation of REEs in plants are affected by numerous biotic factors, such as plant species and genotype, and abiotic factors such as their concentration in the soil and some chemical and physical soil characteristics. They can enter plants via both root and foliage tissues. There are plant species called hyperaccumulators that are able to accumulate significant amounts of REEs without adverse consequences. RREs are not biogenic for higher plants or for other living organisms, but can influence their life processes. Experi?ments show that REEs can be beneficial for growth, yield and biochemical composition of cultivated plants. They can also alleviate some ecological stress in plants. It is not clear enough how they affect human and animal health. The wide-spread application of REEs in different industries as well as in agriculture lead to a constant increase of the concentrations of these elements in the environment. Therefore, studies on the uptake, accumulation, dis?tribution of REEs in cultivated plant species and their entrance into the food chain as well as their stimulating or toxic effect on living organisms, can be very significant in the future.

Discrimination of thermodynamic and kinetic contributions to the heavy rare earth element patterns in metamorphic garnet

AbstractVariations of rare earth element (REE) concentrations in metamorphic garnet are an important source of information of geodynamic and geochemical processes in the deeper Earth. In order to extract this information, the thermodynamic equilibrium and kinetic contributions of the REE uptake in garnet must be distinguished and quantified. Utilizing high‐resolution trace element and μ‐Raman mapping together with combined thermodynamic–geochemical–diffusion models, we demonstrate that the equilibrium and kinetic aspects of the REE uptake in metamorphic garnet can be discriminated by interpreting 2D trace element mapping in a single sample. The heavy (H) REE (Tb to Lu) zoning in the investigated garnet from a high‐pressure blueschist comprises an inner part with an overall decrease from core to inner rim, followed by a concentric zone of HREE enrichment and a drastic HREE decrease towards the outermost rim. The central peak in the garnet core decreases in intensity with decreasing atomic number of the REE. The broad overall shape of this pattern resembles those often observed in metamorphic garnet from different rock types and tectonic settings. Superimposed on this trend is a concentric pattern of minor recurring fluctuations in the HREE concentrations with at least six regularly spaced sets of peaks and troughs along the entire garnet radius. Comparison of the observed inclusion suite, the trace element maps and thermodynamic–geochemical models show that the inner part with decreasing HREE concentrations results from fractional garnet growth in an unchanged mineral assemblage, whereas the REE enrichment zone is caused by the breakdown of titanite. We suggest that the width of the central peak is controlled by the bulk permeability of the interconnected transport matrix and the fraction of matrix minerals that the garnet equilibrates with. The superimposed REE fluctuations result from changing element transport properties of the host rock and mark recurring changes from equilibrium REE uptake to transport‐limited REE uptake in garnet. Such fluctuating element transport properties can be best explained by pulse‐like fluid fluxes that rhythmically change the interconnectivity of the intercrystalline transport matrix. Increasing numbers of published spatially highly resolved REE analyses show that such trace element fluctuations are common in metamorphic garnet indicating that recurring changes in rock permeabilities due to pulsed fluid fluxes are a common phenomenon during metamorphism.

Rare earth element uptake mechanisms in plankton in the Estuary and Gulf of St. Lawrence

The global shift toward green energy alternatives escalates demands for new resources, including rare earth elements (REEs), as per their implications in various green innovations. However, our understanding of their environmental cycle, especially the interactions with aquatic organisms, remains deficient, ultimately hindering environmental protection efforts. Here, we investigate the accumulation of REEs and 18 other elements in bulk and sorted plankton collected with different net mesh sizes (30, 63, 200, 333, 500 μm) in the Estuary and Gulf of St. Lawrence in the summer and winter of 2020. We observed significant correlations between the concentrations of REEs and elements of different charge numbers and ionic radii (Ba, Co, Cs, Fe, Mn, Pb, Rb and V), indicating non-selective uptake of REEs into plankton. All these elements have their highest concentrations in the fluvial corridor and upper estuary, with more significant enrichment in phytoplankton ([La] = 26.4 ± 4.8 mg kg−1) than zooplankton ([La] = 11.6 ± 8.3 mg kg−1). Their concentrations decrease to the minimum in the Gulf of St. Lawrence, especially in zooplankton ([La] = 4.8 × 10−2 ± 3.2 × 10−2 mg kg−1). We also assessed REE patterns to identify differential REE fractionation processes and anomalies. The freshwater plankton exhibits enrichment of middle REEs (MREEs) relative to the light and heavy REEs (LREEs and HREEs), potentially because of the higher binding affinity of MREEs on cellular surface transporters and metal loading effects. In estuarine and marine settings, the REE patterns in biological samples align with suspended particles, exhibiting a linear trend with LREE enrichment. This process is more noticeable in sorted macrozooplankton, which have significant Eu anomalies (Eu/Eu* up to 2), indicating differential incorporation of REEs into the chitin shells. This study highlights the significant enrichment of REEs into freshwater primary producers and the accumulation pathway similar to other inorganic elements.

Rare Earth Elements Uptake by Synthetic Polymeric and Cellulose-Based Materials: A Review.

Contemporary industrial processes and the application of new technologies have increased the demand for rare earth elements (REEs). REEs are critical components for many applications related to semiconductors, luminescent molecules, catalysts, batteries, and so forth. REEs refer to a group of 17 elements that have similar chemical properties. REE mining has increased considerably in the last decade and is starting an REE supply crisis. Recently, the viability of secondary REE sources, such as mining wastewaters and acid mine drainage (AMD), has been considered. A strategy to recover REEs from secondary water-related sources is through the usage of adsorbents and ion exchange materials in preconcentration steps due to their presence in low concentrations. In the search for more sustainable processes, the evaluation of synthetic polymers and natural source materials, such as cellulose-based materials, for REE capture from secondary sources should be considered. In this review, the chemistry, sources, extraction, uses, and environmental impact of REEs are briefly described to finally focus on the study of different adsorption/ion exchange materials and their performance in capturing REEs from water sources, moving from commercially available ion exchange resins to cellulose-based materials.

Atomistic Insights into Structure and Dynamics of Neodymium(III) Complexation with a Bis-lactam Phenanthroline Ligand in the Organic Phase.

Rare-earth elements (REEs) such as neodymium are critical materials needed in many important technologies, and rigid neutral bis-lactam-1,10-phenanthroline (BLPhen) ligands show one of the highest extraction performance for complexing Nd(III) in REE uptake and separation processes. However, the local structure of the complexes formed between BLPhen and Nd(III) in a typical organic solvent such as dichloroethane (DCE) is unclear. Here, we perform first-principles molecular dynamics (FPMD) simulations to unveil the structure of complexes formed by BLPhen with Nd(NO3)3 in the DCE solvent. BLPhen can bind to Nd(III) in either 1:1 or 2:1 fashion. In the 1:1 complex, three nitrates bind to Nd(III) via the bidentate mode in the first solvation shell, leading to the formation of a neutral complex, [Nd(BLPhen)(NO3)3]0, in the organic phase. In contrast, there are two nitrates in the first solvation shell in the 2:1 complex, creating a charged complex, [Nd(BLPhen)2(NO3)2]+. The third nitrate was found to be far away from the metal center, migrating to the outer solvation shell. Our simulations show that the binding pocket formed by the two rigid BLPhen ligands allows ample space for two nitrates to bind to the Nd(III) center from opposite sides. Our findings of two nitrates in the first solvation shell of the 2:1 complex and the corresponding bond distances agree well with the available crystal structure. This study represents the first accurate FPMD modeling of the BLPhen–Nd(III) complexes in an explicit organic solvent and opens the door to more atomistic understanding of REE separations from first principles.

Effect of substrate properties and phosphorus supply on facilitating the uptake of rare earth elements (REE) in mixed culture cropping systems of Hordeum vulgare, Lupinus albus and Lupinus angustifolius

This study presents how phosphate (P) availability and intercropping may influence the migration of rare earth elements (REEs) in legume–grass associations. In a replacement model, Hordeum vulgare was intercropped with 11% Lupinus albus and 11% Lupinus angustifolius. They were cultivated on two substrates, A (pH = 7.8) and B (pH = 6.6), and treated with 1.5 g P m−2 or 3 g P m−2. Simultaneously, a greenhouse experiment was conducted to quantify carboxylate release. There, one group of L. albus and L. angustifolius was supplied with either 200 µmol L-1 P or 20 µmol L-1 P. L. albus released higher amounts of carboxylates at low P supply than L. angustifolius, while L. angustifolius showed the opposite response. Plants cultivated on substrate B accumulated substantially higher amounts of nutrients and REE, compared to substrate A. Higher P supply did not influence the leaf and stem P concentrations of H. vulgare. Addition of P decreased REE accumulation in barley monocultures on alkaline soil A. However, when H. vulgare was cultivated in mixed culture with L. angustifolius on alkaline substrate A with high P supply, the accumulation of REE in H. vulgare significantly increased. Conversely, on acidic substrate B, intercropping with L. albus decreased REE accumulation in H. vulgare. Our findings suggest a predominant effect of soil properties on the soil–plant transfer of REEs. However, in plant communities and within a certain soil environment, interspecific root interactions determined by species-specific strategies related to P acquisition in concert with the plant’s nutrient supply impact REE fluxes between neighbouring plants.

Preliminarily report on rare earth element taphonomy of a Miocene mixed age fossil vertebrate assemblage (Pécs-Danitzpuszta, Mecsek Mts., Hungary): uptake mechanism and possible separation of palaeocommunities

ABSTRACT The sand pit of Pécs-Danitzpuszta is one of the most important mixed Neogene vertebrate localities in Hungary, with older Miocene (Langhian – Serravallian) terrestrial and marine animal remains re-deposited into the upper Miocene (Tortonian) Lake Pannon sediments. Due to the mixed status of the Pécs-Danitzpuszta vertebrate assemblages, limited information is available about the former depositional environment and age of these fossils. However, the rare earth element (REE) composition of the fossil apatite can help to determine the stratigraphic origin and the early depositional environments of unprovenanced vertebrate remains. In this study, the REE composition of more than 60 vertebrate fossils, among them reworked and in situ remains from the Mecsek Mountain, were analysed. The results allowed separation between the Badenian, Sarmatian, and Pannonian aged fossils. The REE content and their distribution also helped us characterise the ancient depositional conditions of the investigated reworked fossils. Furthermore, several different types of vertebrate fossils were analysed, resulting in a large database that helped clarify the likely timings and mechanisms of REE uptake at this locality. Apparent variation in REE chemistry within bones (cortical vs cancellous) and teeth (enamel vs dentine) are best linked to fractionation along the REE series during their incorporation.

Molecular-level understanding of highly selective heavy rare earth element uptake by organophosphorus modified MIL-101(Cr)

Selective separation of rare earth elements (REEs) from solutions of mixed heavy and light metals by solid adsorbents is an important challenge in the fields of water treatment and metal recovery. The main challenge is water instability of many adsorbents, specifically metal–organic frameworks (MOFs), and their low selectivity. Grafting particular organophosphorus compounds (OPCs) on the MIL-101(Cr) MOF can provide both stability and selectivity. When the tributyl phosphate (TBP), bis(2-ethylhexyl) hydrogen phosphate (D2EHPA or HDEHP) and bis(2,4,4-trimethylpentyl)phosphinicacid (Cyanex®-272) OPCs are grafted and applied to mixed-metal aqueous solutions containing Co2+, Ni2+, Cu2+, Zn2+, Nd3+, Gd3+ and Er3+, MIL-101(Cr) offers high selectivity towards the Nd3+, Gd3+ and Er3+ REEs (with stronger affinity towards Er3+). However, the underlying chemistry is unknown and the factors leading to the selectivity remain poorly understood. To uncover the key molecular-level factors, we performed state-of-the-art computational simulations using a combination of high-level density functional theory (DFT), semi-empirical calculations, and configurational sampling of the metal ion-MOF binding modes in aqueous solutions. Our simulation study reproduced the available experimental results, in addition to determining the contributing intermolecular interactions, uptake modes and the most significant structural features for improving selectivity towards the REEs. Therefore, our most important result is rationalization of the mechanism of REE separation by OPC-grafted MOFs using quantum mechanical and electrostatic principles. The results provide guidelines for synthesis of OPC-grafted MIL-101(Cr) structures with enhanced selectivity and stability. Moreover, an efficient computational framework is proposed to facilitate comprehensive modeling of similar systems.