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All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Remote Americium Detection Using an Optical Sensor: A D-Optimal Strategy for Efficient PLS-Based Modeling

A fiber-optic visible–near-infrared absorption spectroscopy system in a glove box was demonstrated for remote quantification of Am(III) (0–500 µM) and HNO 3 (0.1–9 M) using partial least squares regression (PLSR) models. The sensor platform, featuring a simple plug-and-play spectrophotometer, can enable noninvasive, real-time monitoring of actinide process solutions. To establish a flexible PLSR model calibration strategy, a D-optimal design developed using Nd(III) in previous studies was successfully extended to an actinide system with Am(III) to effectively minimize sample set size while maintaining robust prediction performance. The results suggest strong spectral similarities between Nd(III) and Am(III) and validate Nd(III) as an effective optical surrogate for trivalent actinide species. This work also supports the generalizability of a D-optimal training set selection approach for two-factor systems. The PLS1 models for Am(III) and HNO 3 outperformed a PLS2 model and maintained reasonable performance in the presence of interfering U(VI). The resulting sensor system and multivariate approach provides a flexible and scalable solution for process monitoring, control, and safety in diverse nuclear applications.

actinide↗
DOE OSTI2026

A Comparison of Three Neodymium Atomic Data Sets for Kilonova Modeling

We examine the impact of input neodymium (Nd) atomic data on the light curves and spectra of kilonovae (KNe), probing the sensitivity of kilonova observables to the atomic physics of this important lanthanide element. We use the SuperNu Monte Carlo radiative transfer code, simulating a simple semianalytic 1D kilonova (KN) with a pure Nd atmosphere, fixing the radiative transfer method while using input atomic data generated by three different codes: the LANL suite of atomic physics codes, HULLAC, and Autostructure. We see that the choice of atomic data significantly shapes the resulting light curves and spectra. Peak bolometric luminosities differ by a ratio of nearly 1.5 between HULLAC/Autostructure and LANL data sets. Moreover, we observe significant near- to mid-IR differences in the structure of the spectra. We specifically attribute these differences to the choice of atomic data for neutral Nd I. Many of the results here have been adapted from a presentation at “Radiative Transfer and Atomic Physics of Kilonovae” in Stockholm, 2023. We additionally present a LANL data set with energies calibrated to available values in the NIST Atomic Spectra Database, and demonstrate that this calibration also significantly affects IR spectral structure at late time. The substantial differences in KN observables that arise from tuning the atomic data of just one lanthanide element highlight the special attention that must be paid to atomic physics uncertainties when modeling KNe, from AT2017gfo to beyond.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2026

Data-driven Techniques for $v^{e}$ Signal and Background Predictions in NOνA

NOν \nu A is a long baseline neutrino oscillation experiment, using two functionally identical detectors to measure νe \nu_e appearance and νμ \nu_\mu disappearance at the Far Detector (FD) with the NuMI Beam at Fermilab. The Near Detector (ND) measures the beam before oscillations, which will allow us to make a measurement of the signal flux before it has oscillated and the background components which can mimic νe \nu_e at our FD. We use the ND in three different ways to predict the amount of signal and background expected at the FD to partially cancel systematic uncertainties. The background prediction has three components: Charged Current (CC) νμ \nu_\mu , νe \nu_e and Neutral Current (NC) events. We need to determine the fraction of the selected ND sample in each of these components because some oscillate significantly (CC νμ \nu_\mu ) and some do not oscillate at all (NC). This poster will present details of these three data-driven techniques for predicting the FD spectrum.

Yu, Shiqi [Argonne; IIT, Chicago]↗
DOE OSTI2025

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↗
DOE OSTI2025

Recovery and Refining of Rare Earth Elements from Lignite Mine Wastes

The University of North Dakota (UND), in collaboration with a comprehensive team of technical, business and host-site partners, built on prior technology development to complete a front-end engineering and design (FEED) and business planning study to recover and refine rare earth elements (REE) and critical minerals (CM) from North Dakota (ND) lignite mine wastes. The end of project goal was to have an investment quality project and a committed team ready to commercialize the proposed technologies in a future construction and operations phase.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2025

Selective Recovery of Critical Minerals from Simulated Electronic Wastes Via Reaction‐Diffusion Coupling

Abstract Atom‐ and energy‐efficient chemical separations are urgently needed to meet the surging demand for critical materials that has strained supply chains and threatened environmental damage. In this study, we used reaction‐diffusion coupling to separate iron, neodymium, and dysprosium ions from model feedstocks of permanent magnets, which are typically found in electronic wastes. Feedstock solutions were placed in contact with a hydrogel loaded with potassium hydroxide and/or dibutyl phosphate, resulting in complex precipitation patterns as the various metal ions diffused into the reaction medium. Specifically, we observed the precipitation of up to 40 mM of iron from the feedstock, followed by the enrichment of 73 % dysprosium, and the extraction of >95 % neodymium product at a further distance from the solution‐gel interface. We designed a series of experiments and simulations to determine the relevant ion diffusivities, D Nd =5.4×10 −10 and D Dy =5.1×10 −10 m 2 /s, and precipitation rates, k Nd =1.0×10 −5 and k Dy =5.0×10 −3 m 9 mol −3 s −1 , which enabled a numerical model to be established for predicting the distribution of products in the reaction medium. Our proof‐of‐concept study validates reaction‐diffusion coupling as an effective and versatile approach for critical materials separations, without relying on ligands, membranes, resins, or other specialty chemicals.

Wang, Qingpu [Physical and Computational Sciences ↗
DOE OSTI2024

The Critical Influence of Spin–Dry Technique on the Surface Passivation Quality of Crystalline Silicon Solar Cell Structures

This study examines the effects of spin-dry (SD) and N 2 blow-dry (ND) techniques on the quality and surface passivation performance of silicon oxide grown in ozone-dissolved deionized water. The SD method achieves greater oxide thickness uniformity, averaging 1.39 nm ± 4.17% across 49 points, compared to 1.68 nm ± 21.67% for the ND wafers. However, persistently poor passivation of ozonated oxide-grown wafers following the SD process is exhibited, with carrier lifetime, τ eff < 0.3 ms and saturation current density, J 0 (per side) ranging from 26 to 45 fA cm 2 . These findings are analyzed in the context of the fundamental phenomena involved in the drying processes of both techniques. Following this, an optimized spin-drying process is developed, resulting in improved τ eff and J 0 values of 1.4 ms and 5.6 fA cm –2 , respectively. Scanning electron microscopy further confirms that the oxide films dried with the enhanced SD technique are free of pinholes.

14 SOLAR ENERGY↗
DOE OSTI2026

Selective transport of light vs. heavy rare earth elements by sulfate/bisulfate complexes in hydrothermal fluids

Here, this study explores the transport of rare earth elements (REE) in acidic sulfate-bearing hydrothermal fluids and the implications for the fractionation of light/heavy REE in critical mineral deposits. The speciation of Nd (light REE) and Yb (heavy REE) sulfate complexes were determined via in situ Raman spectroscopy using fused SiO 2 capillary cells up to 300 ºC at saturated water vapor pressure and in a hydrothermal diamond anvil cell up to 500 ºC and 540 MPa. The REE monosulfate (REESO 4 + ) and REE disulfate (REE(SO 4 ) 2 - ) species are stable below 150 to 250 ºC but become less stable at higher temperatures, particularly the light REE, due to the decreased solubility of REE sulfate solids. At higher pressure, these REE sulfate complexes display an increased stability field up to 400 ℃. The REE bisulfate complex (REEHSO 4 2+ ) was identified with a wide stability field below 400 ºC for the HREE in acidic Yb 2 (SO 4 ) 3 -bearing solutions, whereas in Nd 2 (SO 4 ) 3 -bearing solutions, the LREE bisulfate complex is restricted to below 100 ℃. These results suggest that bisulfate is a previously unrecognized selective ligand for heavy REE transport at low temperature in acidic oxidized hydrothermal fluids. Such fluids are responsible for hydrothermal alteration in many REE deposits. Prediction of phase stabilities across pressure, temperature, and composition space (P-T- x ) is crucial for predicting the role of aqueous REE sulfate complexes in the mobilization of REE in crustal fluids.

58 GEOSCIENCES↗
DOE OSTI2025

Investigation of residual stress distribution in wire-arc directed energy deposited refractory molybdenum alloy utilizing numerical thermo-mechanical analysis and neutron diffraction method

Directed energy deposition (DED), a metal additive manufacturing (AM) technique, offers higher deposition rates and energy efficiency, making it suitable for fabricating components from refractory molybdenum alloys, such as molybdenum-titanium-zirconium (TZM). However, large thermal gradients and non-equilibrium thermal cycles in DED could generate high residual stress in the component, potentially deteriorating quality and performance. Thus, this study aims to investigate residual stress generation and its distribution in wire-arc DED of TZM thin-wall, utilizing thermo-mechanical analysis and high-fidelity neutron diffraction (ND) method. Two interpass temperatures (50°C and 200°C) have been considered to investigate their impact on residual stress formation. During experiments, in-situ thermal data has been recorded using thermocouples, which have been utilized for calibrating the thermal model. Thermocouple data shows a good agreement with the simulation results, having a difference of less than 10 %. Post-deposition part deformation has been observed, which is measured using a coordinate measuring machine, showing maximum values of 0.93 mm and 0.78 mm for interpass temperatures of 50°C and 200°C, respectively. Numerical predictions of distortion deviated by less than 15% from the experimental results. ND measurement and simulation results indicate that residual stress magnitude and evolution vary across the TZM deposits, revealing microstructural anisotropy in both conditions. Notably, lower interpass temperatures resulted in higher residual stresses, confirmed by experimental and simulation data. Further, this study demonstrated that an integrated experimental and thermo-mechanical analysis can potentially reveal the temperature history, part deformation, and residual stress formation in wire-arc DED TZM alloy.

36 MATERIALS SCIENCE↗
DOE OSTI2024

First-principles investigation of lanthanides diffusion in HCP zirconium via vacancy-mediated transport

The diffusion of lanthanide fission products plays an important role in the growth of the fuel-cladding chemical interaction (FCCI) region in metallic fuels. The use of a Zr interdiffusion barrier may mitigate the transport of lanthanides from the fuel to the cladding, but the efficacy of such a liner is not yet known. In this paper, the stability and vacancy-mediated diffusion of La, Ce, Pr, and Nd in hexagonal close-packed (HCP) Zr is investigated via density functional theory (DFT) calculations and self-consistent mean field (SCMF) analysis. DFT is used to calculate the formation, binding, and migration energies of vacancies and vacancy-solute pairs. The DFT energetics are used in the KineCluE code to calculate the Onsager transport coefficients. La is found to be the fastest diffusing species in HCP Zr and experiences an almost isotropic diffusion behavior. The other three species (Ce, Pr, and Nd) demonstrate anisotropic diffusion where the diffusion in the basal planes is significantly faster than that along the c-axis. Further, the calculated lanthanide diffusivities in HCP Zr are fitted to an Arrhenius relation and the activation energies and prefactors are reported for the first time. Furthermore, the vacancy drag and the segregation tendencies were analyzed using the calculated off-diagonal transport coefficients. According to our vacancy-mediated diffusion model, lanthanides are expected to be enriched at vacancy sinks at low temperatures, while at high temperatures, lanthanides are depleted at sinks and will preferably diffuse into the bulk. The enrichment/depletion transition temperature depends on the diffusion direction (basal or axial) and hence will be controlled by the grain texture and orientation.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Unraveling the solvation phenomena of Ln 3+ cations in room-temperature ionic liquids: A computational study

Rare-earth elements (REEs), classified as critical materials, are difficult to separate due to their similar chemical properties and slight differences in ionic radius. Room-temperature ionic liquids (RTILs) have gained significant attention for REE separation because of their unique physicochemical properties and environmental advantages. In this study, we have investigated the solvation mechanisms of two RE cations (Ln 3+ ), Nd 3+ (light REE) and Yb 3+ (heavy REE), in two 1-butyl-3-methylimidazolium ([BMIM] + )-based RTILs using bis(trifluoromethylsulfonyl)imide ([NTf 2 ] − ) and acetate ([OAc] − ) as the respective anions, employing classical molecular dynamics (MD) simulations and density functional theory (DFT) techniques. From MD simulations, it is evident that Ln 3+ cations are primarily solvated by RTIL anions in the first solvation shell, while [BMIM] + cations form the second solvation shell with their numbers depending on the size and composition of the first solvation shell. The neutralizing [NO 3 − ] counterions are mainly solvated by [BMIM] + cations in their first solvation shell. Relative free energy change of solvation calculations using thermodynamic integration (TI) method indicate that Yb 3+ is more strongly solvated than Nd 3+ in both RTILs, a trend further supported by DFT calculations. While both methods predict consistent qualitative behavior, differences in models and energy evaluations lead to variations in absolute values. Overall, this study provides a comprehensive understanding of the solvation behavior of Ln 3+ cations in RTILs, demonstrating a stronger solvation preference for the heavy Ln 3+ cation (Yb 3+ ). In conclusion, these findings have implications for the design of RTIL-based separation processes for REEs.

Ash, Tamalika [Ames Lab., and Iowa State Univ., Am↗
DOE OSTI2025

Recovering high-purity uranyl nitrate from simulated used nuclear fuel dissolver solutions by crystallization: rejecting technetium

The separation of U from Tc and other problematic fission product elements like Mo and Ru, along with Sr, Zr, Cs, and Nd, has been achieved via the crystallization of uranyl nitrate hexahydrate (UNH). Rejection of technetium as pertechnetate anion ( 99 TcO 4 – ) is an especially important feature of this system, as it otherwise tends to follow U (VI) in extractive separations. It also raises the salient question regarding why this oxoanion cannot replace nitrate within the crystalline lattice of UNH. Results showed high-yield (>90 %), high-purity (>99 %) recovery of U as UNH from solutions containing 99 TcO 4 – by simple reduction of temperature from 60°C to 20°C. There was no observable interaction of 99 TcO 4 – with UO 2 2+ . The addition of other cations like, Sr 2+ , Zr 4+ , Cs + , and Nd 3+ , also did not form secondary, contaminant solid phases, leaving the > 99 % of the fission product elements in the mother liquor, while the U was recovered at > 90 %. Similarly, Mo and Ru, when added to the mixture, were shown to behave as the other fission-product elements, remaining in the mother liquor during crystallization. As a result, DFT calculations showed that, despite the higher binding strength of TcO 4 – , HMoO 4 – , and BiO 3 – with the UO 2 2+ cation compared to NO 3 – , the hydrogen-bonding network of the two coordinated ions and four waters of hydration in the UNH crystal structure is the driving force for the high specificity of this separation.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Crystal Growth of Quaternary Rare Earth Selenosilicates by Using the Flux-Assisted Boron Chalcogen Mixture Method: Investigation of Their Magnetic and Optical Properties

A series of rare earth magnesium selenosilicates, RE3Mg 0.5 SiSe 7 (RE = Ce, Pr, Nd, Sm, Gd, Tb, Dy) were obtained as single crystal using the flux assisted boron chalcogen mixture (BCM) method. The structures of the crystals were determined by single-crystal X-ray diffraction. The RE3Mg 0.5 SiSe 7 series crystallizes in the hexagonal crystal system in the space group P6 3 . Polycrystalline powders were synthesized to perform physical property measurements. Magnetic measurements over the 2–300 K temperature range reveal that Ce 3 Mg 0.5 SiSe 7 and Gd 3 Mg 0.5 SiSe 7 exhibit paramagnetic behavior with negative Weiss constants (θ W = −14.50, θ W = −6.13 K, respectively). The optical properties of RE 3 Mg 0.5 SiSe 7 (RE = Ce, Pr, Nd, Sm, Gd) were measured by ultraviolet–visible (UV–vis) diffuse reflectance. Density functional theory (DFT) electronic structure calculations were performed. Furthermore, a second harmonic generation measurement was performed on a polycrystalline powder of Ce 3 Mg 0.5 SiSe 7 and was found to be SHG active with an efficiency of 0.11 times the standard potassium dihydrogen phosphate (KDP).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

X-ray Scintillating Lanthanide-Based Coordination Polymers

Reported are the syntheses and characterization of 25 lanthanide-containing coordination polymers exhibiting four structure types: type I′: [Ln(TFTP) 1.5 (bpy)] (Ln = La 3+ –Nd 3+ ), type I: [Ln(TFTP) 1.5 (bpy)(H 2 O)] (Ln = Sm 3+ –Lu 3+ ), type II′: [Pr(TFTP) 1.5 (phen)], and type II: [Ln(TFTP) 1.5 (phen)(H 2 O)] (Ln = Nd 3+ –Yb 3+ , excluding Pm). These compounds feature lanthanide metal cations bound to tetrafluoroterephthalate linkers (TFTP) and either, 2,2′-bipyridine (bpy) or 1,10-phenanthroline (phen) capping ligands. Initial calculations using crystallographic data revealed large void spaces, ranging from 86 Å 3 in type I to 333 Å 3 in type II. Yet, adsorption isotherm data indicate very little gas uptake of both materials with a BET surface area of 9 m 2 /g for I-Tb (8) and 19 m 2 /g for II-Tb (20). X-ray irradiation of I-Eu (6), II-Eu (18), I-Tb (8), and II-Tb (20) produced visible red and green emission, respectively. Furthermore, radioluminescence studies of both type I and II with Sm 3+ , Eu 3+ , and Tb 3+ metal centers indicate that both structure types featuring Tb 3+ are brighter than those with Eu 3+ or Sm 3+ . Notably, structure type I with Tb 3+ is the brightest scintillator with a relative luminosity of 1.7× that of bismuth germanate (BGO).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Crystallographic Snapshots of Pre- and Post-Lanthanide Halide Hydrolysis─Reaction Products Captured by the 4-Amino-1,2,4-triazole Ligand

Reactions of lanthanide(III) chloride salts with 4-amino-1,2,4-triazole (4-NH 2 -1,2,4-Triaz) in azole melts have led to the isolation of both hydrolysis and non-hydrolysis products in the same synthesis with the inclusion of a variety of ligands, anions, and water, allowing us to capture crystallographic snapshots of different forms and intermediate hydrolysis fragments. The structural studies reported here include anhydrous and hydrated nonhydrolyzed complexes which were isolated alongside hydrolysis products giving oxide/hydroxide lanthanide(III) dimers, tetramers, and ultimately hexamers. The compounds isolated include [Nd 2 Cl 6 (μ 2 -4-NH 2 -1,2,4-Triaz) 4 (4-NH 2 -1,2,4-Triaz) 2 ], [Ce 2 Cl 4 (μ 2 -Cl) 2 (μ 2 -4-NH 2 -1,2,4-Triaz) 4 ] n , [Ce 2 (µ 2 -Cl) 4 (µ 2 -OH) 2 (µ 2 -4-NH 2 -1,2,4-Triaz) 2 ] n , [Ln 4 Cl 4 (µ 2 -Cl) 4 (µ 3 -OH) 4 (µ 2 -4-NH 2 -1,2,4-Triaz) 4 ] n •2nH 2 O (Ln = Ce, Nd), and [Ce 6 Cl 6 (µ 6 -O 0.5 )(µ 3 -Cl 0.5 ) 4 (µ 3 -Cl 0.75 ) 3 (µ 3 -OH) 0.75 (µ 2 -4-NH 2 -1,2,4-Triaz) 12 ((OH 2 ) 0.25 ) 2 ] 2 [CeCl 6 ][Cl 9 ]•xH 2 O. In all complexes all lanthanide atoms are pairwise connected via one or more 4-NH2-1,2,4-Triaz ligands and sometimes additional Cl - anions.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2026

Electrochemical Recovery of Rare-Earth Elements from Coal Fly Ash Using Ionic Liquids as both Extractant and Electrolyte

Rare-earth elements (REEs) are critical for medical technologies, electronics, and clean energy. Coal fly ash (CFA), a byproduct of coal combustion, offers a promising alternative REE source. However, efficient extraction and separation of REEs from CFA remain challenging due to the complex composition of CFA. This study introduces a sustainable method for REE recovery using a recyclable ionic liquid, betainium bis(trifluoromethylsulfonyl)imide ([Hbet]- [Tf 2 N]), which serves both as the extractant from CFA and as the electrolyte in electrodeposition. In the first stage, [Hbet][Tf 2 N] preferentially extracts REEs from CFA through leaching. In the second stage, the REE-enriched ionic liquid undergoes electrochemical deposition using amperometry techniques, where REEs are reduced and deposited onto the electrode. The deposition experiments were conducted from −0.5 to −2.0 V vs a Pt quasireference electrode in a three-electrode setup comprising titanium as the working electrode and platinum as both the reference and counter electrodes. Varying the applied potential enabled potential-dependent preferential REE deposition. At −0.5 V, neodymium (Nd) showed preferential recovery, reaching 25% with a separation factor of 37 over other REEs. In contrast, applying a more negative potential increased overall deposition, yielding ∼50% Nd recovery and 10−20% recovery for the remaining REEs. After recovery, the ionic liquid was regenerated and reused for a subsequent electrochemical recovery cycle. Overall, this study demonstrates a feasible approach for REE recovery from CFA waste, with potential to enhance resource utilization within the REE supply chain.

coal fly ash↗
DOE OSTI2025

Elucidation of an Unusually Long Pu–N Bond in a Plutonium(III)-Tetrazolate Complex

Four trivalent, f-element tetrazolate hydrate complexes [M(H 2 O) 9 ](Hdtb) 3 ·nH 2 O (Nd1, n = 7 and Pu1, n = 9; dtb 2– = 1,3-di(tetrazolate-5-yl)benzene) and [M(Hdtb)(H 2 O) 8 ](dtb)·11H 2 O (Nd2 and Pu2) were prepared using metathesis reactions. These complexes contain hydrated M(III) cations, but in the latter complexes, Nd2 and Pu2, one of the water molecules has been displaced by a long interaction between the M(III) cation and a Hdtb – anion. Notably, the Pu(III)–N bond in Pu2, representing the longest IX Pu(III)–N ( IX = nine coordinate) bond reported has a length of 2.8338(15) Å and is slightly shorter than the Nd(III)–N bond length of 2.8425(13) Å in Nd2. Analysis of bond lengths, Wiberg bond indices (WBI), natural localized molecular orbitals (NLMOs), and quantum theory of atoms in molecules (QTAIM) reveals that the metal contribution to the Pu(III)–N bond is marginally greater than that of the Pu(III)–OH 2 bonds in Pu2 and the Nd(III)–N bond in Nd2. Thus, this rather long M–N interaction provides an example where the expectation that An(III) compounds exhibit greater covalency with soft donor ligands compared to harder ligands fails. Furthermore, the absorption spectra of Pu1 and Pu2 further support this observation, highlighting a surprising degree of similarity in their electronic structures.

Covalent bonding↗
DOE OSTI2024

Adsorption of Neodymium, Dysprosium, and Ytterbium to Goethite under Varying Aqueous Chemistry Conditions

The adsorption of rare earth elements (REEs) to iron oxides can regulate the mobility of REEs in the environment and is heavily influenced by water chemistry. This study utilized batch experiments to examine the adsorption of Nd, Dy, and Yb to goethite under varying pH, electrolyte (type and concentration), and concentrations of dissolved inorganic carbon and citrate. REE adsorption was strongly influenced by pH, with an increase from essentially no adsorption at pH 3.0 to nearly complete adsorption at pH 6.5 and higher. Citrate enhanced the adsorption of REEs at low pH (<5.0), likely by forming goethite-REE-citrate ternary surface complexes. However, citrate inhibited the adsorption of REEs at higher pH (>5.0) by forming aqueous REE-citrate complexes. Ionic strength had a small influence on REE adsorption, and the presence of dissolved inorganic carbon had no discernible effect. Equilibrium adsorption was interpreted with a triple-layer surface complexation model (SCM). The selection of surface complexation reactions was guided by extended X-ray absorption fine structure spectra. An SCM with a single bidentate inner-sphere surface complexation reaction for Nd and two inner-sphere surface complexation reactions (one monodentate and one bidentate reaction) for Dy and Yb effectively simulated adsorption across a broad range of conditions in the absence of citrate. Accounting for the effects of citrate on REE adsorption required the addition of up to two ternary REE-citrate-goethite surface complexes. The SCM can enable predictions of REE transport in subsurface environments that have goethite as an important adsorbent mineral. Furthermore, this predictive capability could contribute to identifying potential REE sources and facilitating efficient extraction of REEs.

58 GEOSCIENCES↗