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Rare earth elements in river waters

To characterize the input to the oceans of rare earth elements (REE) in the dissolved and the suspended loads of rivers, the REE concentrations were measured in samples of Amazon, Indus, Mississippi, Murray-Darling, and Ohio rivers and in samples of smaller rivers that had more distinct drainage basin lithology and water chemistry. It was found that, in the suspended loads of small rivers, the REE pattern was dependent on drainage basin geology, whereas the suspended loads in major rivers had relatively uniform REE patterns and were heavy-REE depleted relative to the North American Shale composite (NASC). The dissolved loads in the five major rivers had marked relative heavy-REE enrichments, relative to the NASC and the suspended material, with the (La/Yb)N ratio of about 0.4 (as compared with the ratio of about 1.9 in suspended loads).

Goldstein, Steven J.↗

Rare Earth Element Measurements of Melilite and Fassaite in Allende Cai by Nanosims

The rare earth elements (REEs) are concentrated in CAIs by approx. 20 times the chondritic average [e.g., 1]. The REEs in CAIs are important to understand processes of CAI formation including the role of volatilization, condensation, and fractional crystallization [1,2]. REE measurements are a well established application of ion microprobes [e.g., 3]. However the spatial resolution of REE measurements by ion microprobe (approx.20 m) is not adequate to resolve heterogeneous distributions of REEs among/within minerals. We have developed methods for measuring REE with the NanoSIMS 50L at smaller spatial scales. Here we present our initial measurements of REEs in melilite and fassaite in an Allende Type-A CAI with the JSC NanoSIMS 50L. We found that the key parameters for accurate REE abundance measurements differ between the NanoSIMS and conventional SIMS, in particular the oxide-to-element ratios, the relative sensitivity factors, the energy distributions, and requisite energy offset. Our REE abundance measurements of the 100 ppm REE diopside glass standards yielded good reproducibility and accuracy, 0.5-2.5 % and 5-25 %, respectively. We determined abundances and spatial distributions of REEs in core and rim within single crystals of fassaite, and adjacent melilite with 5-10 m spatial resolution. The REE abundances in fassaite core and rim are 20-100 times CI abundance but show a large negative Eu anomaly, exhibiting a well-defined Group III pattern. This is consistent with previous work [4]. On the other hand, adjacent melilite shows modified Group II pattern with no strong depletions of Eu and Yb, and no Tm positive anomaly. REE abundances (2-10 x CI) were lower than that of fassaite. These patterns suggest that fassaite crystallized first followed by a crystallization of melilite from the residual melt. In future work, we will carry out a correlated study of O and Mg isotopes and REEs of the CAI in order to better understand the nature and timescales of its formation process and subsequent metamorphic history.

Ito, M.↗

Rare Earth Element Partitioning in Lunar Minerals: An Experimental Study

The partitioning behavior of rare earth elements (REE) between minerals and melts is widely used to interpret the petrogenesis and geologic context of terrestrial and extra-terrestrial samples. REE are important tools for modelling the evolution of the lunar interior. The ubiquitous negative Eu anomaly in lunar basalts is one of the main lines of evidence to support the lunar magma ocean (LMO) hypothesis, by which the plagioclase-rich lunar highlands were formed as a flotation crust during differentiation of a global-scale magma ocean. The separation of plagioclase from the mafic cumulates is thought to be the source of the Eu depletion, as Eu is very compatible in plagioclase. Lunar basalts and volcanic glasses are commonly depleted in light REEs (LREE), and more enriched in heavy REEs (HREE). However, there is very little experimental data available on REE partitioning between lunar minerals and melts. In order to interpret the source of these distinctive REE patterns, and to model lunar petrogenetic processes, REE partition coefficients (D) between lunar minerals and melts are needed at conditions relevant to lunar processes. New data on D(sub REE) for plagioclase, and pyroxenes are now available, but there is limited available data for olivine/melt D(sub REE), particularly at pressures higher than 1 bar, and in Fe-rich and reduced compositions - all conditions relevant to the lunar mantle. Based on terrestrial data, REE are highly incompatible in olivine (i.e. D much less than 1), however olivine is the predominant mineral in the lunar interior, so it is important to understand whether it is capable of storing even small amounts of REE, and how the REEs might be fractionatied, in order to understand the trace element budget of the lunar interior. This abstract presents results from high-pressure and temperature experiments investigating REE partitioning between olivine and melt in a composition relevant to lunar magmatism.

McIntosh, E. C.↗

Electrokinetic Rare Earth Element Purification

I, Kyle McCarthy, am traveling to Boston, MA for the Materials Research Society conference. At the conference, I will give an oral presentation on research findings from Energy and Homeland Security LDRD "A New, Green Approach to Rare Earth Element (REE) Purification Based on Electrokinetics." in talk titled "Electrokinetic Rare Earth Element Purification." I will also attend other live presentations and conduct professional networking. This fits within Sandia's energy security mission.

McCarthy, Kyle Patrick [Sandia National Laboratori↗

Electrokinetically Driven Rare Earth Element Separation by Coated Capillary Arrays

I, Kyle McCarthy, am traveling to Austin, TX for the TechConnect World Innovation conference. At the conference, I will give an poster presentation on research findings from Energy and Homeland Security LDRD "A New, Green Approach to Rare Earth Element (REE) Purification Based on Electrokinetics." titled "Electrokinetically Driven Rare Earth Element Separation..." I will also attend other live presentations and conduct professional networking. This fits within Sandia's energy security mission.

Merrill, Laura Christine [Sandia National Laborato↗

Design and Optimization of Processes for Recovering Rare Earth Elements from End-of-Life Hard Disk Drives

In this conference paper, we propose a superstructure-based approach to finding the optimal pathways for recovering rare earth elements in their commercialized rare earth oxide form from end-of-life HDDs. The proposed superstructure was modeled as a MILP optimization problem, selecting the net present value as the objective function. Whenever possible, costing data taken from the literature was used to inform this mode. However, due to the novelty of this research area data were often not available thus requiring the generation of flowsheets that were implemented in Aspen Plus. To establish the base case optimal result, projections for the number of EOL HDDs in the U.S. available for recycling and estimates of the projected rare earth oxide prices over the lifetime of the plant were used to inform the model. The model was then expanded to include the recycling of EOL HDDs generated prior to the beginning of plant production (period ranging from 2006 through 2024).

Laliwala, Chris↗

Recycling Rare Earth Elements from End-of-Life Electric and Hybrid Electric Vehicle Motors

In this paper, we propose a superstructure-based approach to finding the optimal pathways for recovering rare earth elements in their commercialized rare earth oxide form from end-of-life EV and HEV motors. The proposed superstructure was modeled as a MILP optimization problem, selecting the net present value as the objective function. Whenever possible, costing data taken from the literature was used to inform this mode. However, due to the novelty of this research area data were often not available thus requiring the generation of flowsheets that were implemented in Aspen Plus.

Laliwala, Chris↗

Rare Earth Elements (REEs) Measurement in Coal and Rock Mineral Matrices

Although critical minerals including rare earth elements (REEs) can be analyzed in laboratory by some established and reliable laboratory based analytical techniques, their in-situ measurements in the field have always been challenging. For identification of REE-rich sites and REEs distribution measurement, portable field applicable technologies are paramount. As Laser-induced breakdown spectroscopy (LIBS) has enormous potential for field measurement, it has been explored for REEs measurements by many research groups. However, most of the studies are still dealing with simulated samples with traditional bench top experiments. In real world, REEs are available in various types of natural complex matrices in low content depending on the geographical locations. Considering this, LIBS has been evaluated for REE measurement in two different complex coal and rock mineral matrices representing some natural REE-rich sites. In addition, multiple samples collected from some natural sites in Wyoming, USA were experimented by using NETL’s bench top as well as miniaturized prototype setups for REE measurements.

Bhatt, Chet R.↗

Rare Earth Element Detection and Quantification in Coal and Rock Mineral Matrices

As global demand for rare earth elements (REEs) increases, maintaining the production and supply chain is critical. Technologies capable of being used in the field and in situ in the subsurface for rapid REE detection and quantification facilitates the efficient mining of known resources and exploration of new and unconventional resources. Laser-induced breakdown spectroscopy (LIBS) is a promising technique for rapid elemental analysis both in the laboratory and in the field. Multiple articles have been published evaluating LIBS for detection and quantification of REEs; however, REEs in their natural deposits have not been adequately studied. In this work, detection and quantification of two REEs, La and Nd, have been studied in both synthetic and natural mineral matrices at concentrations relevant to REE extraction. Measurements were performed on REE-containing rock and coal samples (natural and synthetic) utilizing different LIBS instruments and techniques, specifically a commercial benchtop instrument, a custom benchtop instrument (single- and double-pulse modes), and a custom LIBS probe currently being developed for in situ, subsurface, borehole wall detection and quantification of REEs. Plasma expansion, emission intensity, detection limits, and double-pulse signal enhancement were studied. The limits of detection (LOD) were found to be 10/14 ppm for La and 15/25 ppm for Nd in simulated coal/rock matrices in single-pulse mode. Signal enhancement of 3.5 to 6-fold was obtained with double-pulse mode as compared to single-pulse operation.

La detection↗

Compositional and phase relations among rare earth element minerals

A review is presented that mainly treats minerals in which the rare-earth elements are essential constituents, e.g., bastnaesite, monazite, xenotime, aeschynite, allanite. The chemical mechanisms and limits of REE substitution in some rock-forming minerals (zircon, apatite, titanite, garnet) are also derived. Vector representation of complex coupled substitutions in selected REE-bearing minerals is examined and some comments on REE-partitioning between minerals as related to acid-based tendencies and mineral stabilities are presented. As the same or analogous coupled substitutions involving the REE occur in a wide variety of mineral structures, they are discussed together.

Burt, D. M.↗

Compositional and phase relations among rare earth element minerals

This paper discusses the compositional and phase relationships among minerals in which rare earth elements (REE) occur as essential constituents (e.g., bastnaesite, monazite, xenotime, aeschynite, allanite). Particular consideration is given to the vector representation of complex coupled substitutions in selected REE-bearing minerals and to the REE partitioning between minerals as related to the acid-base tendencies and mineral stabilities. It is shown that the treatment of coupled substitutions as vector quantities facilitates graphical representation of mineral composition spaces.

Burt, D. M.↗

Technoeconomic Assessment of Phosphoric Acid and Rare Earth Element Recovery from Phosphoric Acid Sludge

Sustainability faces many challenges, including the availability of materials necessary for technological advancement. Rare earth elements (REEs), for example, are key materials for several manufacturing industries that can unlock renewable energy and sustainable development. In this study, a decanter centrifuge has been employed to successfully separated phosphoric acid and REE-containing particles from phosphoric acid sludge with concentrations ranging from 1000 to 2200 ppm REEs. Operating efficiently with up to 35 wt.% solids, the centrifuge was demonstrated to achieve approximately 95% phosphoric acid recovery and 90% REE recovery in a single pass, eliminating the need for additional processing steps. This breakthrough supports a proposed rare earth oxide (REO) recovery process integrating phosphoric acid (PA), elemental phosphorus (P4), and REO into two potential pathways: PA-REO and PA-P4-REO. These processes aim to reintroduce recovered phosphoric acid into the main product to significantly increase output and revenue. Post-separation, phosphorus-rich particles can be converted to P4, while REE-containing solids undergo further treatment including acid leaching, extraction/stripping, precipitation, and calcination to produce a marketable REO material. Technoeconomic analysis indicates promising profitability, with the PA-REO process showing a delta net present value (ΔNPV) of USD 441.8 million over a 12-year period and expected return within a year of construction, while the PA-P4-REO process yields a ΔNPV of USD 178.7 million over a 12-year return period. Both pathways offer robust financial prospects and demonstrate the feasibility of commercial-scale REO recovery from phosphoric acid sludge, offering an economically feasible approach to produce REEs for future sustainable development challenges related to sustainability.

36 MATERIALS SCIENCE↗

Sustainable recovery of Rare Earth Elements (REEs) from coal and coal ash through urban mining: A Nature Based Solution (NBS) for circular economy

The demand for rare earth elements (REEs) has surged in recent years, driven by their crucial role in various industrial applications and their uneven geological distribution. As a result, urban mining from secondary resources, particularly coal and coal ash, has gained traction as a sustainable solution within a circular economy framework. This study highlights the significant presence of REEs in coal and coal ash, revealing that certain samples contain REE concentrations that rival traditional ores. Notably, coal ash has the potential to yield approximately 312,000 tons of REEs annually, far exceeding global demand. The research delves into advanced techniques for analyzing REEs, including elemental, isotopic, and mineralogical studies. Additionally, it explores innovative extraction methods such as the use of green solvents, nature-based solutions, and bioleaching and biosorption. By leveraging coal and its byproducts as secondary resources, this study underscores the opportunity to reduce dependence on conventional mining, enhancing the sustainability of REE recovery. Here, a comprehensive literature review was conducted to highlight technological advancements and emerging opportunities that can address current challenges in this field.

Circular economy↗

Life Cycle Inventories and Data Gap Analysis for Rare Earth Elements: Neodymium and Dysprosium from Mining to Magnets

The United States demand for Neodymium-Iron-Boron (NdFeB) magnets, produced from rare earth elements (REEs) such as (Nd) and Dysprosium (Dy), far exceeds its nascent domestic production capacity, rendering it reliant on vulnerable global supply chains dominated by China. To guide research and development investments in securing U.S. REE supply, defensible benchmark metrics across environmental, economic, and social dimensions are needed. In this study, we built globally-representative, process-based cradle-to-cradle life cycle inventories for Nd and Dy in NdFeB magnets lifecycles, encompassing primary material acquisition, beneficiation, smelting and refining, metal processing, specialty alloy and chemical transformation, subcomponent manufacturing, consumer application (use phase) and end-of-life management. We carried out detailed literature review, and applied process engineering principles to build industry-representative upscaled life cycle inventories for both metals. We used these models to conduct bottom-up literature review and gap analysis on existing literature, compilation of data sources for each life cycle stage (and transformations where necessary), and a preliminary technoeconomic analysis (TEA)/life cycle costing analysis (LCCA). Findings from this work emphasize the need for metal specific, representative REE LCIs to establish robust benchmarks for advancing sustainable REE technologies and guiding R&D in REE supply chains.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Sustainable extraction of rare earth elements from coal fly ash leachates using a recyclable ionic liquid

The growing demand for rare earth elements (REEs) has prompted interest in their recovery from alternative sources such as coal fly ash (CFA). This study explores the ionic liquid (IL) betainium bis(trifluoromethylsulfonyl)imide, [Hbet][Tf 2 N], for selective extraction of REEs from leachates of a Class C CFA. While previous studies have demonstrated the effectiveness of using [Hbet][Tf 2 N] to extract REEs from different types of CFA in direct ash-IL systems, this study investigates four CFA leachates prepared using HCl, HNO 3 , H 2 SO 4 , and citrate. Extraction experiments were conducted across varying pH levels and with additives such as ascorbic acid and betaine. Among the systems tested, [Hbet][Tf 2 N] achieved REE recoveries of 51% and 47% from the HCl and citrate leachates, respectively, comparable to 49% REE recovery in ash-IL extraction. Co-extraction of bulk elements was significantly reduced in the leachate-IL systems. Optimal REE extraction occurred near pH 11, and addition of ascorbic acid effectively suppressed iron co-extraction without compromising REE recovery. Recycling experiments demonstrated that [Hbet][Tf₂N] retains its performance over five cycles with manageable losses. These results reveal the promise of [Hbet][Tf 2 N] for effectively recovering REEs from leachates of solid wastes, highlighting its applicability as a sustainable strategy for other aqueous REE feedstocks.

chemistry↗

Bacterial Biomining Rare Earth Elements in Abandoned Coal Mine Drainage: Solubilization and Sequestration

Bacteria can be used to biomine rare earth elements (REEs) domestically from abandoned coal-mine drainage (AMD) solids. Pennsylvania has ~11,000 abandoned mines, with ~500 AMD passive remediation systems that precipitate AMD REE rich solids onsite. In passive systems, REEs, co-precipitate with manganese (Mn), accumulating as solids that can produce a valuable leachate when resolubilized. REEs like lanthanum (La) are used in battery technology. Microbial metabolic changes that co-resolubilize Mn and REEs could result in an affordable release process that does not require chemical additives and the select sequestering of REEs like La allow for the selective purification from a mixed REE composition. Currently, the microbial mechanisms that contribute to mass REE resolubilization and selective sequestration are poorly understood. We have isolated bacteria (Bacillus mycoides JR07 and Bacillus pseudomycoides KB7) that solubilize Mn oxide, La oxide, and AMD solids by acidogenesis. We have determined that isolates JR07 and KB7 solubilize the La from AMD PRS solids by their production of organic acids. Preliminary results show methylotrophic bacterial isolate B3 can take up soluble La(III), giving an avenue to purification of La from a rich REE leachate. Determining the microbial metabolism and genes involved in the mass resolubilization of REEs and selective biomining of La(III) is crucial to optimize the biomining of AMD solids. Our work addresses the growing need to develop novel REE recovery methods from domestic sources.

microbiology↗

Mobility of heavy rare earth elements in magmatic-hydrothermal systems: Experimental determination of DyPO 4 solubility in supercritical fluids

Dysprosium (Dy) is part of the heavy rare earth elements (REE) and a critical component in the production of high-performance super magnets used in wind turbines, electric vehicles, and other green technologies. The HREE phosphate, xenotime, is commonly associated with hydrothermal systems, where the mobility, fractionation, and deposition of REE are controlled by the stability of aqueous complexes and solubility of REE minerals which depend on temperature, pressure, and fluid composition (salinity, pH, and ligand availability). Here, we conducted a series of synthetic DyPO 4 solubility experiments in NaCl-HCl-bearing aqueous solutions (pH of 2 at 25 °C) from 500 to 700 °C and 1.5 kbar using externally heated pressure vessels. DyPO 4 displays a strong prograde solubility with temperature across all studied fluid salinities (0–0.5 m NaCl). The DyPO₄ solubility isotherms at 500 °C, 600 °C, and 700 °C show a complex relationship with salinity where DyPO₄ solubility is highest (39.2–1552 ppm at 500–700 °C) in 0 m NaCl solutions, decreases strongly (21–331 ppm at 500–700 °C) in the 0.06 m NaCl solutions and remains relatively constant in the 0.25 m (42.8–248 ppm) and 0.5 m NaCl (40.2–124 ppm) solutions. Thermodynamic modeling suggests that pH increases as a function of temperature and salinity, and controls solubility due to the stability of chloride complexes (i.e., DyCl +2 and DyCl 2 + ) at 500–600 °C, transitioning to hydroxyl complexes (i.e., Dy(OH) 3 0 ) dominating at 700 °C and relatively alkaline pH. Comparison with NdPO 4 solubility data indicates that the light REE in monazite is significantly more soluble than the heavy REE in xenotime in saline fluids at high temperature (500–700 °C), implying efficient light/heavy REE fractionation in supercritical fluids. The lower solubility of DyPO 4 relative to NdPO 4 suggests that at high temperatures, acidic (pH 2–4), low-salinity (∼5 wt% NaCl) fluids will favor the precipitation of xenotime over monazite as it will cool from 700 °C to below 500 °C. These observations align with paragenetic mineral assemblages in NYF pegmatites (e.g., Baveno, Italy), where xenotime commonly immobilizes heavy REE during the high-temperature hydrothermal stages.

58 GEOSCIENCES↗