Adsorption Of Rare Earth Elements Research Articles

Opportunities and Constraints of the Adsorption of Rare Earth Elements onto Pyrolytic Carbon-Based Materials: A Mini-Review

Rare earth elements (REEs), comprising seventeen metallic elements, including lanthanides, scandium, and yttrium, are indispensable for modern technological industries due to their unique properties. However, their supply is critically risky for the European Union, with 95% of global production concentrated in China, Brazil, Vietnam, Russia, India, and Australia. This mini-review examines the adsorption of REEs onto pyrolytic carbon-based materials as a sustainable recovery method from secondary raw materials. The review covers different types of carbon-based adsorbents used in several research works, such as activated carbon, chars, and biochar, and discusses their adsorption mechanisms and influencing factors. Comparative analyses of adsorption capacities highlight the significance of surface area and functionalization in enhancing adsorption efficiency. Despite promising results, the variability in adsorption performance due to experimental conditions and the scarcity of real-world application studies are noticed. This review underscores the need for further research using real e-waste leachates to validate the practical applicability of pyrolytic carbon-based adsorbents for REEs’ recovery, aiming for an economically and environmentally sustainable solution.

Construction of Ion-Imprinted Graphene Oxide Mixed-Matrix Membranes for Selective Adsorption and Separation of Tm3.

Efficient adsorption and separation of rare earth from other similar rare earth wastewater has become an urgent demand for resource utilization of ion-type rare earth minerals in China. Herein, thulium (Tm) ion-imprinted graphene oxide (GO)-doped polyether sulfone (PES) membranes (GO-TII/PES-2 membranes) were prepared, in which ion-imprinted graphene oxide was applied as an efficient Tm3+ ionic ligand in the imprinted layer and polyether sulfone was applied as a carrier in the membrane matrix to achieve the selective adsorption and separation of Tm3+ and neighboring rare earth ions. Combined with an ion rectifier, the separation and purification performances of Tm3+ were explored. The separation factors β(Tm3+/Tb3+), β(Tm3+/Sm3+), β(Tm3+/Nd3+), and β(Tm3+/Ce3+) in the dynamic adsorption process increased significantly from 1.22, 1.04, 1.04, and 1.02 for nonimprinting to 3.07, 3.91, 3.91, and 3.33 for imprinted membranes. The GO-TII/PES-2 membrane adsorbed about three times more Tm3+ than the nonionic-imprinted (GO-NII/PES) membrane by adding a color developer and quantifying Tm3+ based on a fast and easy UV-photometric method. After eight dynamic permeations, the adsorption of Tm3+ by the GO-TII/PES-2 membrane decreased by only 13%, indicating that the membrane has good reuse performance. Additionally, the investigation examined the influence of Tm3+ on wheat seed germination, underscoring its potential application in agriculture and the importance of adsorbing and separating rare earth ions.

Interpretation of vertical migration and enrichment processes of rare earth elements (REEs) in ion-adsorption-type mineralization in Japan based on REE speciation analyses

Typical vertical profiles of ion-adsorption-type rare earth element (REE) deposits discovered in southwest Japan were studied by conducting speciation analyses, including X-ray absorption fine structure and laser-induced fluorescence spectroscopy combined with transmission electron microscopy and adsorption/desorption experiments. The results revealed that REE speciation, migration, and enrichment in weathered granite is largely controlled by soil pH, which in turn controls the variable charges of kaolinite, the REE host phase. Both the distribution coefficient Kd and the soil pH increase with depth. As a result, (i) REE dissolution and migration occur in the near-surface acidic environment of the upper layers, where hydroxyls of kaolinite basal surfaces and edges are deprotonated to a lesser degree, and (ii) REEs accumulate in the relatively high-pH environment below the surface, where hydroxyls of kaolinite basal surfaces and edges are deprotonated to a larger degree, producing REE adsorption sites with variable charges. An increase of soil pH to greater than 6 in deeper layers promotes inner-sphere complexation of REEs. Although inner-sphere complexation inhibits the ion-exchange extraction of REEs, the inner-sphere complexes can be still extracted by lowering the pH of the extraction solution. This fact, which indicates that the adsorption of both inner- and outer-sphere complexes is reversible, is important in terms of both (i) understanding vertical REE profiles in which the pH varies and (ii) the efficient recovery of REEs from REE-enriched layers at all depths in weathered granite.

Selective separation and recovery of rare-earth elements (REEs) from acidic solutions and coal fly ash leachate by novel TODGA-Impregnated organosilica media

Rare-earth elements (REEs) are essential in a wide range of applications including magnets and satellite technology, with demand driven by geopolitical factors. While multiple techniques exist for REE recovery including solvent extraction and selective precipitation, solid–liquid extraction offers key advantages in selectivity, scalability, and recyclability. N, N, N′, N′-tetraoctyl diglycolamide (TODGA) is a tridentate ligand widely used in solvent extraction, but the incorporation in a solid support to separate individual lanthanides from acid solutions remains largely unexplored. A novel TODGA-organosilica sorbent material was developed and tested to evaluate recovery of 17 elements (REEs and thorium) in terms of selectivity, kinetics, and equilibrium isotherms in 0.01 to 15.9 M nitric acid. Characterization of the new sorbent was performed before and after sorption using FTIR, XPS, and SSA techniques to help elucidate sorption mechanisms and limiting variables. REE adsorption increased from 1.26 mg g−1 to 10 mg g−1 with nitric acid concentrations of 0.01 M and 15.9 M, respectively. TODGA-organosilica exhibits high selectivity towards heavy REEs (Dy to Lu), with minimal sorption of lighter REEs (Ce to Gd). Batch adsorption experiments confirm pseudo-second-order kinetics and a Langmuir adsorption isotherm with TODGA binding to REEs in a 3:1 complex. A packed bed column study confirmed the high selectivity of TODGA-impregnated organosilica towards heavy REEs and a proof-of concept experiment with coal fly ash leachate shows high selectivity for REEs over Al, Fe, and Ca present in several orders of magnitude higher concentrations. Fractionation was observed where loading cycle effluent contained 84 % light REEs while strip cycle effluent contained 80 % heavy REEs. More than 90 % of loaded REEs were successfully stripped with water as the stripping agent.

Elucidating the selective adsorption of heavy rare earth by phosphate modified silica: The cooperation of pore confinement and surface structure regulating

Rare earths are considered strategic metals, with heavy rare earth elements of greater importance due to their supply and utilization field. However, efficient separation of heavy rare earth elements is a great challenge as the similar physicochemical properties between light and heavy rare earths. In this study, the highly efficient adsorbents with confinement effect are synthesized by the modification of MCM-41 materials with dimethyl clodronate (NP2) and methylene dichlorophosphate (NDP2). The adsorbents were characterized by XRD, TEM, SEM-EDS, N2 adsorption–desorption, FTIR, TG, 13C NMR, and XPS. It was discovered that the pore size of MCM-41 affected markedly the adsorption selectivity, and the cooperation of the organic adsorption center and pore confinement of MCM-41 support enabled the selective adsorption of heavy rare earth ion. The adsorbent modified by NP2 exhibited high adsorption selectivity toward heavy rare earth ions (Lu3+) with the increase in pore size of MCM-41. In contrast, the expanded pore of MCM-41 enhanced the selectivity of light rare earth ions for the NDP2 modified adsorbents. The distribution coefficient of Lu3+ adsorption over NP2-MCM-41(III) adsorbent reached 20,132 mL g−1 and the separation factor of Lu to La reached 82.17. DFT calculations revealed that a vital driving force for the selective adsorption of Lu was the gap of binding energy between Lu and La complexes with the surface NP2/NDP2 groups. The synergy of pore confinement and organic functional groups in adsorbents in this paper offers a valuable strategy for designing efficient materials in the separation of rare earth elements.

Impact of particle size and associated minerals on rare earth desorption and incorporation mechanisms in a South American ion-adsorption clay

This research delves into the intricate nexus of particle size, mineralogical composition, surface attributes, elemental mapping, and rare earth element (REE) adsorption mechanisms within an ion-adsorption clay sample from South America. The investigation entails the fractionation of the ion-adsorption clay into three size categories: S1 (< 0.25 mm), S2 (0.25–0.5 mm), and S3 (0.5–2 mm). Each fraction undergoes meticulous characterization to unveil its elemental composition, mineralogical composition, surface area, morphological characteristics, elemental mapping, and the mechanisms governing REE incorporation. The results indicate that S1 has 31% physiosorbed, 8% chemisorbed, and 61% mineralized REEs, while S2 has 40% physiosorbed, 5% chemisorbed, and 55% mineralized REEs, and S3 has 24% physiosorbed, 5% chemisorbed, and 71% mineralized REEs. The physisorbed REEs are attributed to the presence of kaolinite, conducive to mostly physisorption. In terms of grain size and REE content/type relationship, the results show that REE content decreases with increasing grain size; however, there is not a clear trend in terms of REE occurrence modes with grain size. Heavy rare earth elements (HREEs) are discernibly favored in adsorption over light rare earth elements (LREEs). This preference is underpinned by the weathering processes that led to the formation of ion-adsorption clay, which facilitated the transport and accumulation of HREEs. Notably, the ion-adsorption clay encompasses a substantial content of mineralized REEs, necessitating more demanding extraction methodologies, such as acid baking followed by water leaching if complete extraction of all REEs is desired. Among the desorbable REEs, physisorption dominates, encompassing over 80% of the total. Chemisorbed REEs exhibit versatility in association with various minerals, encompassing kaolinite, quartz, and goethite. In essence, this study unveils the intricate interplay between particle dimensions, mineralogical constitution, surface attributes, and REE adsorption modes within this ion-adsorption clay sample. The ion-adsorption clay in this study contains a significant portion of mineralized REEs that cannot be extracted using the mild conditions typically employed for the desorption process. Additionally, the REE concentration in this ion-adsorption clay is notably higher than the average found in clay deposits worldwide, reaching levels comparable to those of regolith deposits in China, which are a major global source of REEs. This remarkable concentration of REEs, along with the unique modes of their occurrence in this deposit, presents a significant interest to the scientific community.

Efficient Capture and Release of the Rare-Earth Element Neodymium in Aqueous Solution by Recyclable Covalent Organic Frameworks.

Rare-earth elements (REEs) are present in a broad range of critical materials. The development of solid adsorbents for REE capture could enable the cost-effective recycling of REE-containing magnets and electronics. In this context, covalent organic frameworks (COFs) are promising candidates for REE adsorption due to their exceptionally high surface area. Despite having attractive physical properties, COFs are heavily underutilized for REE capture applications due to their limited lifecycle in aqueous acidic environments, as well as synthetic challenges associated with the incorporation of ligands suitable for REE capture. Here, we show how the Ugi multicomponent reaction can be leveraged to postsynthetically modify imine-based COFs for the introduction of a diglycolic acid (DGA) moiety, an efficient scaffold for REE capture. The adsorption capacity of the DGA-functionalized COF was found to be more than 40 times higher than that of the pristine imine COF precursor and more than four times higher than that of the next-best reported DGA-functionalized solid support. This rationally designed COF has appealing characteristics of high adsorption capacity, fast and efficient capture and release of the REE ions, and reliable recyclability, making it one of the most promising adsorbents for solid-liquid REE ion extractions reported to date.

Interface Modulation of 2D Superlattice Heterostructures with Oxygen-enriched Sites and Dissolution Restraint for Effective Rare-earth Elements Extraction

Effective recovery of rare earth elements from wastewater is crucial for the modern industry, as well as for protecting the human health and ecosystem. Nevertheless, it is still challenging to realize efficient and selective low-concentration rare earth extraction in systems containing high levels competing metal ions. Here, we report on the fabrication of two-dimensional superlattice heterostructures (VOGO-x) through the alternating restacking of VOPO4 nanosheets and GO-PDDA nanosheets via electrostatic self-assembly. The meticulously organized molecular scale of superlattice heterostructures enable the full exposure of accessible adsorption sites and facilitate the transport of rare earth ions, meanwhile the abundant oxygen-containing phosphate groups within the interlayer can realize selective rare earth ions extraction. Furthermore, the tunable interlayer interaction can promote structure stability to prevent dissolution. Consequently, VOGO-11 possesses excellent rare earth adsorption performance, with a saturated adsorption capacity (Nd(III) 631.52 mg/g, Dy(III) 689.48 mg/g, Lu(III) 716.06 mg/g), high utilization rate of adsorption sites and short adsorption equilibrium time of simply 10 min in the REE aqueous solution. Furthermore, VOGO-11 exhibits outstanding selective rare earth adsorption ability over a wide range of metal ions in the low-concentration simulated wastewater and actual leaching tailings. These results demonstrate the material’s promising potential in capturing rare earth ions and pave the way to the development of two-dimensional superlattice heterostructures through interface modulation for effective rare earth extraction.

Indigenous microbial influence on REE enrichment and fractionation in South China weathering crusts: Insights from experimental simulations

The activity of microorganism plays an important role on the enrichment, migration and fractionation of rare earth elements (REEs) in the supergene environment. To investigate the characteristics of indigenous microorganisms on the enrichment and fractionation of REEs, we studied the adsorption efficiencies of REEs by 30 indigenous microbial strains that were isolated and cultured from the weathering profile of a regolith-hosted REE deposit in South China. Most microbial strains exhibited high adsorption efficiencies for REEs, ranging from 2.3 to 42.9 mg g−1. Notably, the taxonomic classification of microorganisms significantly influenced the adsorption selectivity. Gram-positive bacteria exhibited a pronounced enrichment of the heavy REEs, while gram-negative bacteria showed no obvious adsorption preference. The tetrad effects were observed in REE adsorption patterns of gram-negative bacteria and fungi; however, fungi demonstrated a much higher affinity for light and medium REEs. Chemically modified microbial cells were employed to investigate the adsorption mechanism, revealing that distinct functional groups of microbial cells corresponded to the adsorption preference of microorganisms towards REE. Carboxyl and phosphate groups contributed to a relatively high adsorption capacity for light REEs and heavy REEs, respectively. The findings of our study suggest that the distinct composition of microbial groups may exert a significant influence on the biogeochemical cycle of REE in weathering profiles.

Grain size control on organo-clay complexation and REE fractionation in the Paleozoic strata of the Permian Basin (West Texas, U.S.A.)

As a major component of mudstone, clay minerals are known to conserve organic matter (OM) as well as a range of trace elements through the mechanisms of adsorption, encapsulation, and/or intercalation. The associations of the clay minerals on one hand and trace elements and OM on the other hand impact the diagenetic evolution of such rocks and is of substantial importance for their characterization and assessment. Subsurface core samples collected from Late Paleozoic mudstone within the Permian Basin of Texas were separated into four grain size fractions (&amp;gt;2 µm, 2 to 1 µm, 1 to 0.6 µm, and &amp;lt;0.6 µm) to determine the clay mineralogy, OM abundances, and rock geochemistry using a suite of diffraction, spectroscopic, and chemical analysis. All separates were largely consisted of illite-smectite (I-S), illite-tobelite-smectite (I-T-S), mica/illite and chlorite coupled with some minor quartz and feldspar. The smectite component of I-S was shown to increase with decreasing grain size fractions. Additionally, t he rise in the content of smectite interlayers correlated with an increase in the total organic carbon (TOC) content towards the finest grain size separates in all samples. This suggested that a significant portion of the TOC content resided in the fraction below 2 µm and that smectite interlayers promoted the preservation of OM. Rare earth elements (REE) concentrations were found to be the highest in the finest grain size separates and align with an increased content of smectite interlayers, denoting a plausible interaction between the two. Further on, REE and TOC concentrations display a significant positive correlation in all size fractions and increase with respect to smectite interlayer content. This three-component relation suggests the REE adsorption to illite-smectite was likely promoted by OM. Understanding the close relation between the clay minerals, OM, and trace element content is indicative of polyvalent cationic bridging, ligand exchange, and organo-metallic complexation, which eventually l eads to the enrichment of OM and fractionation of REE in mudstone.

Highly selective recovery of rare earth elements from mining wastewater using phyto-synthesized biochar dispersed iron nanoparticles

Recovery of rare earth elements (REEs) from secondary sources such as mining wastewater has attracted much recent attention due to the rising global demand for REEs and the need to environmentally protect potentially contaminated mine sites. One significant issue it that most adsorbents proposed for removal and/or recovery of REEs are not generally selective for REEs. In this study, biochar dispersed iron nanoparticles synthesized using a plant extract (BC-FeNPs) were successfully used for the selective recovery of REEs from mining wastewater, where the Kd values were Nd(III) (918 mL∙g−1), Eu(III) (1253 mL∙g−1), Tb(III) (1119 mL∙g−1), Dy(III) (1032 mL∙g−1), Lu(III) (1898 mL∙g−1), compared to only 23.9 mL∙g−1 for Zn(II). The maximum adsorption efficiency of REEs for the composite was higher than the constituent parts being 88.4 % for BC-FeNPs, but only 8.72 % for biochar and 82.4 % for FeNPs, respectively. FTIR, XPS and Zeta potential analysis suggested that the observed selective adsorption of REEs, involved interactions of REEs with O and N, as well as ion-exchange with H+ from the biochar and capping layer, as well as electrostatic interactions. The desorption efficiency of bound REEs from BC-FeNPs was > 85 % when using acetic acid, and was attributed to efficient competitive ion exchange. Pearson correlation analysis further demonstrated that the adsorption mechanism included ion complexation, ion exchange and electrostatic adsorption, while the desorption mechanism was mainly via ion exchange. Overall, BC-FeNPs has significant potential to practically recover REEs from mining wastewater having demonstrated excellent reusability after five adsorption–desorption cycles.

Adsorption of rare earth elements (Ce3+, La3+, and Nd3+) and recovery from phosphogypsum leachate using a novel ZSM-5 zeolite

ZSM-5 zeolite is a multifunctional material highly efficient for adsorbing ions. Our ZSM-5 was synthesized by employing a nucleating gel as a structure-directing agent, followed by homogenization and hydrothermal treatment. The as-prepared ZSM-5 was physicochemically characterized to assess its properties. Next, the as-prepared zeolite was employed as an adsorbent to remove rare earth elements, REEs from synthetic solutions and real phosphogypsum leachate under batch mode operation. As expected, the ZSM-5 adsorbent was discovered to be highly microporous with abundant surface functionalities, which could positively impact REE adsorption. The adsorption data indicated a high affinity between ZSM-5 and all three REEs with rapid kinetics and high adsorption capacities. The modeling study suggested that the adsorption kinetic data were well fitted by Avrami-fractional order, and Liu described the equilibrium data. The maximum adsorption capacity for Ce3+, La3+, and Nd3+ were 99.42 mg g−1, 96.43 mg g−1, 118.10 mg g−1, respectively. Further, the thermodynamic analysis revealed that the interaction between ZSM-5 and Ce3+, La3+, and Nd3+ was favorable, spontaneous, and endothermic. The efficiency of ZSM-5 adsorbent was also studied in recovering several REEs from leachate of phosphogypsum wastes, and the data results proved its potency to do so. The findings reported in this work support the idea that ZSM-5 can be successfully used as an adsorbent to recover REEs from synthetic and real samples.

Overview of Functionalized Porous Materials for Rare-Earth Element Separation and Recovery.

The exceptional photoelectromagnetic characteristics of rare-earth elements contribute significantly to their indispensable position in the high-tech industry. The exponential expansion of the demand for high-purity rare earth and related compounds can be attributed to the swift advancement of contemporary technology. Nevertheless, rare-earth elements are finite and limited resources, and their excessive mining unavoidably results in resource depletion and environmental degradation. Hence, it is crucial to establish a highly effective approach for the extraction and reclamation of rare-earth elements. Adsorption is regarded as a promising technique for the recovery of rare-earth elements owing to its simplicity, environmentally friendly nature, and cost-effectiveness. The efficacy of adsorption is contingent upon the performance characteristics of the adsorbent material. Presently, there is a prevalent utilization of porous adsorbent materials with substantial specific surface areas and plentiful surface functional groups in the realm of selectively separating and recovering rare-earth elements. This paper presents a thorough examination of porous inorganic carbon materials, porous inorganic silicon materials, porous organic polymers, and metal-organic framework materials. The adsorption performance and processes for rare-earth elements are the focal points of discussion about these materials. Furthermore, this work investigates the potential applications of porous materials in the domain of the adsorption of rare-earth elements.

Adsorption of Rare Earth Elements at Modified Saponite

Adsorption of Rare Earth Elements at Modified Saponite

Desorption of rare earth elements biosorbed on Euglena mutabilis suspensions and biofilms

AbstractIncreasing demand for rare earth elements (REEs) has stimulated research on novel recovery methods from sources like industrial effluents. Our recent study demonstrated that algal biofilms are good candidates for the adsorption of REEs and that the extracellular polymeric substances (EPS) within the biofilm were a key accumulator of REEs. In this work, we measured the desorption kinetics, extents, and selectivity of REEs from the algae Euglena mutabilis in suspensions and biofilms using aqueous solutions of HCl at pH between 1.5 and 4, and Na2EDTA at pH 5. We examined the potential for reusing suspended and biofilm biomass for repeated adsorption–desorption cycles. The desorption kinetics were similar for suspensions and biofilms, with equilibrium being reached within 20 min. The extent of desorption was higher in biofilms with 86% and 95% desorption, compared to suspensions which had 72% and 74% desorption using HCl and Na2EDTA, respectively. We postulate that the difference between suspensions and biofilms is attributed to the binding sites in the EPS matrix of the biofilm being more readily protonated than those at the algal cell wall surface. Heavy REEs were found to preferentially desorb at pH 4 over lighter REEs. After 3 repeated adsorption–desorption cycles, the adsorption capacity of biofilms increased by 280% and 80% using HCl and Na2EDTA, respectively, compared to an 80% decrease in biosorption capacity for the suspension. The increase in biofilm biosorption capacity was attributed to the simultaneous desorption of divalent cations alongside REEs from the EPS increasing the number of available binding sites.

Adsorption of the rare earth elements cerium, lanthanum, and neodymium onto ZSM-5 zeolite: A statistical physics approach

The recovery of rare earth elements (REE) is essential to meet the growing demand for these resources and promote the reuse of available resources. This study investigated the potential of ZSM-5 zeolite in the recovery of trivalent ions of cerium, lanthanum and neodymium under conditions of pH 6 and temperatures between 298 and 328 K. REE equilibrium isotherms were analyzed using five statistical physics models. The results indicate that removing all REE occurs predominantly in monolayers, as these models showed better prediction performance (coefficient of determination > 0.97 and mean squared error < 18.0). The best model determined that lanthanum and neodymium have one adsorption energy, while cerium has two adsorption energies involved in the process. The predominant functional groups are those containing silicon. Increasing temperature causes an increase in the number of REE ions captured per functional group, which reduces the adsorption space available on the surface. The model parameters indicate that the adsorption of these ions implies a multi-ionic mechanism (number of ions adsorbed per site greater than 1) and is an exothermic process. Based on the calculated adsorption capacities at saturation, the order of preference in adsorption can be established: neodymium > cerium > lanthanum. The adsorption energies indicate that the process occurred mainly due to physical forces since all energy values are below 40 kJ mol−1. The study’s results led to the proposal of a mechanism for the adsorption of REE on ZSM-5 zeolite, which highlights the predominance of electrostatic interactions and complex formation, which result in the formation of a monolayer on the adsorbent’s surface.

Gravity-Driven Separation for Enrichment of Rare Earth Elements Using Lanthanide Binding Peptide-Immobilized Resin.

Rare Earth Elements (REEs) constitute indispensable raw materials and are employed in a diverse range of devices, including but not limited to smartphones, electric vehicles, and clean energy technologies. While there is an increase in demand for these elements, there is a global supply challenge due to limited availability and geopolitical factors affecting their procurement. A crucial step in manufacturing these devices involves utilizing highly pure REEs, often obtained through complex and nonsustainable processes. These processes are vital in isolating individual REEs from mixtures containing non-REEs and other REEs. There exists an urgent requirement to explore alternative techniques that enable the selective recovery of REEs through more energy-efficient processes. To overcome the limitations mentioned above, we developed a microbead-based technology featuring immobilized lanthanide binding peptides (LBPs) for the selective adsorption of REEs. This technology does not require the utilization of external stimuli but uses gravity-based separation processes to separate the bound REE from the unbound REE. We demonstrate this technology's potential by enriching two relevant REEs (Europium and Terbium). Additionally, we propose a mechanism whereby REEs bind selectively to a particular LBP, leveraging the distinctive physicochemical characteristics of both the REE and the LBP. Moreover, these LBPs exhibit no binding affinity toward other frequently encountered industrial ions. Finally, we demonstrate the recovery of REEs through a change in system conditions and assess the reusability of the microbeads for subsequent adsorption cycles. We anticipate that this approach will address the challenges of REE recovery and demonstrate the potential of biomolecular strategies in advancing sustainable resource management.

Transport dynamics of rare earth elements in weathering crust soils

In modern industries, rare earth elements (REEs) are considered as essential metals and invaluable natural resources. Ion-adsorption deposits (IADs) are repositories of REE in the weathering crust soils, in which REEs are adsorbed on clay minerals. In the last few decades, the mining of REEs from IADs has caused substantial environmental damage owing to the overuse of leaching agents for the desorption and transport of REEs in weathering crust soils. These environmental issues have sparked extensive research interest in modeling REE transport dynamics in weathering crust soils. Nevertheless, because current models treat REE adsorption and transport independently, they do not accurately describe REE transport dynamics. Therefore, in this study, a unified workflow that synergizes adsorption and transport dynamics is proposed to predict REE transport. The adsorption of REEs on IADs was found to follow the Freundlich isotherm with the coefficient of determination exceeding 0.9826. The adsorption capacities of La3+, Sm3+, Er3+, and Y3+ reach 1.3127, 1.4423, 1.5793, and 1.1061 mg g−1 at 300 ppm, respectively. For the breakthrough curve, an advection–dispersion–adsorption–equation (ADAE) model was developed and utilized to accurately and reliably predict REE transport dynamics in soil columns. It was found the saturation time of REEs in soils is 39.22, 44.15, 50.64, and 32.17 h, respectively at 2 mL min−1 and decreased with the increase of flow velocity. The upper and lower limits of REE transport are ADAE-Freundlich and ADAE-Toth. More importantly, the model was applied to simulate REEs transport in field-scale weathering crusts over 100 years and predict REE accumulation in the highly weathered layered, which is found in natural weathering crusts. The qualitative prediction of REE transport dynamics in weathering crusts may help fundamentally lower the usage of leaching agents and mitigate concomitant the environmental impacts of mining.

Recovery of rare earth elements from mine wastewater using alginate microspheres encapsulated with zeolitic imidazolate framework-8

There is increasing demand and interest in efficient methods for the recovery of rare earth elements (REEs) from wastewater because of the growing concerns associated with the negative impacts of REEs-rich waste discharged on pristine ecosystems. Here, we designed a ZIF-8@ALG composite hydrogel by encapsulating zeolitic imidazolate frameworks-8 (ZIF-8) into sodium alginate and poly (vinyl alcohol) double cross-linked networks (ALG) for the recovery of REEs from mine wastewater. ZIF-8@ALG showed exceptional REEs adsorption performance with the most superior separation factor (Ho/Mn) of 597.5. For the REEs considered, the ZIF-8@ALG composite exhibited a preference for heavy REEs with high adsorption efficiencies (65.3 ∼ 97.2%) and distribution coefficients (2045.5 ∼ 28500.0 mL·g−1). Adsorption involved a combination of electrostatic attraction, complexation and ion exchange mechanisms. REEs adsorbed on ZIF-8@ALG could also be desorbed using sodium citrate via ion-exchange and complexation, thus achieving efficient REEs recovery. In addition, ZIF-8@ALG was stable and reusable, maintaining effective adsorption in wastewater over four consecutive cycles, where the optimal adsorption efficiency reached 80.0%. Overall, this study provided an effective and feasible method for the recovery of REEs in mine wastewater, and confirmed that ZIF-8-based materials have significant potential for REEs recovery applications in wastewater engineering treatment.

Rare Earth Element Adsorption to Clay Minerals: Mechanistic Insights and Implications for Recovery from Secondary Sources.

The energy transition will have significant mineral demands and there is growing interest in recovering critical metals, including rare earth elements (REE), from secondary sources in aqueous and sedimentary environments. However, the role of clays in REE transport and deposition in these settings remains understudied. This work investigated REE adsorption to the clay minerals illite and kaolinite through pH adsorption experiments and extended X-ray absorption fine structure (EXAFS). Clay type, pH, and ionic strength (IS) affected adsorption, with decreased adsorption under acidic pH and elevated IS. Illite had a higher adsorption capacity than kaolinite; however, >95% adsorption was achieved at pH ∼7.5 regardless of IS or clay. These results were used to develop a surface complexation model with the derived binding constants used to predict REE speciation in the presence of competing sorbents. This demonstrated that clays become increasingly important as pH increases, and EXAFS modeling showed that REE can exist as both inner- and outer-sphere complexes. Together, this indicated that clays can be an important control on the transport and enrichment of REE in sedimentary systems. These findings can be applied to identify settings to target for resource extraction or to predict REE transport and fate as a contaminant.