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All sourcesNASA NTRSDOE OSTI
NASA NTRS1979

Condensation and fractionation of rare earths in the solar nebula

The condensation behavior of the rare earth elements in the solar nebula is calculated on the basis of the most recent thermodynamic data in order to construct a model explaining group II rare earth element patterns in Allende inclusions. Models considered all involve the removal of large fractions of the more refractory heavy rare earth elements in an early condensate, followed by the condensation of the remainder at a lower temperature. It is shown that the model of Boynton (1975) in which one rare earth element component is dissolved nonideally in perovskite according to relative activity coefficients can not reasonably be made to fit the observed group II patterns. A model in which two rare earth components control the patterns and dissolve ideally in perovskite is proposed and shown to be able to account for the 20 patterns by variations of the perovskite removal temperature and the relative proportions of the two components.

Davis, A. M.↗
NASA NTRS1996

A Glass Spherule of Questionable Impact Origin from the Apollo 15 Landing Site: Unique Target Mare Basalt

A 6 mm-diameter dark spherule, 15434,28, from the regolith on the Apennine Front at the Apollo 15 landing site has a homogeneous glass interior with a 200 microns-thick rind of devitrified or crystallized melt. The rind contains abundant small fragments of Apollo 15 olivine-normative mare basalt and rare volcanic Apollo 15 green glass. The glass interior of the spherule has the chemical composition, including a high FeO content and high CaO/Al2O3, of a mare basalt. Whereas the major element and Sc, Ni, and Co abundances are similar to those of low-Ti mare basalts, the incompatible elements and Sr abundances are similar to those of high-Ti mare basaits. The relative abundance patterns of the incompatible trace elements are distinct from any other lunar mare basalts or KREEP; among these distinctions are a much steeper slope of the heavy rare earth elements. The 15434,28 glass has abundances of the volatile element Zn consistent with both impact glasses and crystalline mare basalts, but much lower than in glasses of mare volcanic origin. The glass contains siderophile elements such as Ir in abundances only slightly higher than accepted lunar indigenous levels, and some, such as Au, are just below such upper limits. The age of the glass, determined by the Ar-40/Ar-39 laser incremental heating technique, is 1647 +/- 11 Ma (2 sigma); it is expressed as an age spectrum of seventeen steps over 96% of the Ar-38 released, unusual for an impact glass. Trapped argon is negligible. The undamaged nature of the sphere demonstrates that it must have spent most of its life buried in regolith; Ar-38 cosmic ray exposure data suggest that it was buried at less than 2m but more than a few centimeters if a single depth is appropriate. That the spherule solidified to a glass is surprising; for such a mare composition, cooling at about 50 C/s is required to avoid crystallization, and barely attainable in such a large spherule. The low volatile abundances, slightly high siderophile abundances, and the young age are perhaps all most consistent with an impact origin, but nonetheless not absolutely definitive.

Ryder, Graham↗
DOE OSTI2023

Investigating radioactive negative ion production via double electron capture

The relative cross sections for radioactive negative ion production via double electron capture have been measured for collisions between a 40 keV projectile beam of uranium-238 and potassium vapor. This was performed at the collinear resonance ionization spectroscopy (CRIS) experiment at CERN-ISOLDE and is a step towards measuring the electron affinities (EAs) of elements that cannot be efficiently produced in negative ion sources at radioactive ion beam (RIB) facilities. This includes short-lived radioactive isotopes that have low production quantities and heavy and superheavy elements that systematically have smaller EAs than work functions of available ion source materials. Negative ions are particularly sensitive to electron–electron correlation effects, which make such studies ideal for benchmarking atomic structure models that go beyond the independent particle model. While the EAs of most light elements have been measured, experimental investigations on heavier elements, namely the actinides, remain scarce due to their radioactive nature and production difficulty. By developing negative ion production by charge exchange, we aim to make these studies feasible at RIB facilities.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2023

The forward-backward asymmetry and differences of partial moments in inclusive semileptonic $B$ decays

Global fits to moments of kinematic distributions measured in inclusive semileptonic B\rightarrow X_c l \nu_l B → X c l ν l enable the determination of the Cabibbo-Kobayashi-Maskawa matrix element \left|V_{cb}\right| | V c b | together with non-perturbative matrix elements of the heavy quark expansion. In current fits, only two distinct kinematic distributions are employed and, as a consequence, higher moments of these distributions need to be taken into account to extract the relevant non-perturbative matrix elements. The moments of a given distribution are highly correlated and experimental uncertainties increase for higher moments. To address these issues, Turczyk suggested the inclusion of the charged lepton forward-backward asymmetry \mathcal{A}_{FB} 𝒜 F B in global fits, since it provides information on non-perturbative parameters beyond the commonly used moments. It is possible to construct differences of partial moments of kinematic distributions, which can provide additional information on the non-perturbative parameters beyond \mathcal{A}_{FB} 𝒜 F B and are studied in this work for the first time. Further, experimental cuts on the four-momentum transfer square are studied and are shown to preserve the shape of the angular distribution, in contrast to commonly used cuts on the lepton energy. Finally, the impact of final-state radiation and experimental lepton identification requirements on measurements of \mathcal{A}_{FB} 𝒜 F B and differences of partial moments are discussed.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
NASA NTRS2009

Structural/Radiation-Shielding Epoxies

A development effort was directed toward formulating epoxy resins that are useful both as structural materials and as shielding against heavy-ion radiation. Hydrogen is recognized as the best element for absorbing heavy-ion radiation, and high-hydrogen-content polymers are now in use as shielding materials. However, high-hydrogen-content polymers (e.g. polyethylene) are typically not good structural materials. In contrast, aromatic polymers, which contain smaller amounts of hydrogen, often have the strength necessary for structural materials. Accordingly, the present development effort is based on the concept that an ideal structural/ heavy-ion-radiation-shielding material would be a polymer that contains sufficient hydrogen (e.g., in the form of aliphatic molecular groups) for radiation shielding and has sufficient aromatic content for structural integrity.

Connell, John W.↗
DOE OSTI2022

Crystal Chemistry and Thermodynamics of HREE (Er, Yb) Mixing in a Xenotime Solid Solution

Rare earth elements (REEs), the 15 naturally occurring lanthanides plus yttrium and scandium, are ubiquitously used in modern life as they are critical components of many advanced devices and technologies. However, the demand for REEs is not equal, with the heavy rare earth elements (HREEs) having a higher demand. Xenotime (HREEPO 4 ) is an important HREE ore mineral and globally is an economical source of HREE. Most of the crystallographic and thermodynamic properties of xenotime endmembers have been elucidated by calorimetric, solubility, and high-pressure studies. Yet, in natural systems, endmembers are rarely encountered, and instead, REE solid solutions are more commonly observed. Here, we characterize the crystal chemistry, thermodynamics of HREE mixing, and high-temperature material behaviors and thermochemistry of a synthetic erbium (Er)-ytterbium (Yb) binary xenotime solid solution (Er (x) Yb (1-x) PO 4 ) using a suite of experimental techniques, including X-ray fluorescence spectroscopy, synchrotron X-ray powder diffraction implemented with Rietveld analysis, Fourier transform infrared spectroscopy coupled with attenuated total reflectance, Raman spectroscopy, thermogravimetric analysis coupled with differential scanning calorimetry, and high-temperature oxide melt drop solution calorimetry. Our results shed light on the formation of natural xenotimes and lay the foundation for their industrial applications as thermal coating materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2019

Unravelling Complex Geologic Histories Using U–Pb and Trace Element Systematics of Titanite

Unravelling the spatio-temporal evolution of orogenic terranes requires a comprehensive understanding of the duration and extent of metamorphic events and hydrothermal alteration. Commonly used minerals such as zircon and monazite may not fully record geological histories in complex tectonic settings because their elemental constituents do not react under many metamorphic and metasomatic conditions. Here, we complement the current geochronological record of the Capricorn Orogen, Western Australia, with titanite U–Pb geochronology and geochemistry of felsic intrusive rocks to draw conclusions about the use of titanite in understanding the evolution of orogenic terranes. Because titanite usually incorporates common-Pb and may be variably reset by multiple metamorphic and hydrothermal events, a workflow is provided here for the systematic and robust interpretation of titanite U-Pb data. The addition of trace element data in titanite is particularly effective for differentiating whether a grain is igneous, recrystallized or metamorphic. We have developed several petrogenetic indices to differentiate these three types of titanite using Zr-in-titanite temperature, Th/U, Th/Pb, Al/(Al + Fe), light to heavy rare earth element ratio, and Eu anomalies. The addition of trace element geochemistry can also highlight anomalously radiogenic (sup 207)Pb/(sup 206)Pb reservoirs. Utilization of our workflow in the Capricorn Orogen reveals that titanite ages from the same samples as published zircon U–Pb data range from coeval to several hundreds of Myr of age difference between the two minerals. Titanite geochronology and trace element geochemistry indicates ~20 Myr of previously unrecognized prolonged cooling for the Capricorn Orogeny to ca. 1750 Ma. The spatial extent of the ca. 1210–1170 Ma part of the Mutherbukin Tectonic Event is also broadened significantly farther north and south than previously recognized. Incorporating titanite geochronology and trace geochemistry with more commonly used techniques (e.g., zircon and monazite petrochronology) extends our ability to resolve the complete history of large-scale orogenic terranes.

Hugo K. H. Olierook↗
NASA NTRS1996

Trace Element Zoning and Incipient Metamictization in a Lunar Zircon: Application of Three Microprobe Techniques

We have determined major (Si, Zr, Hf), minor (Al, Y, Fe, P), and trace element (Ca, Sc, Ti, Ba, REE, Th, U) concentrations and Raman spectra of a zoned, 200 microns zircon grain in lunar sample 14161,7069, a quartz monzodiorite breccia collected at the Apollo 14 site. Analyses were obtained on a thin section in situ with an ion microprobe, an electron microprobe, and a laser Raman microprobe. The zircon grain is optically zoned in birefringence, a reflection of variable (incomplete) metamictization resulting from zo- nation in U and Th concentrations. Variations in the concentrations of U and Th correlate strongly with those of other high-field-strength trace elements and with changes in Raman spectral parameters. Concentrations of U and Th range from 21 to 55 ppm and 6 to 31 ppm, respectively, and correlate with lower Raman peak intensities, wider Raman peaks, and shifted Si-O peak positions. Concentrations of heavy rare earth elements range over a factor of three to four and correlate with intensities of fluorescence peaks. Correlated variations in trace element concentrations reflect the original magmatic differentiation of the parental melt approx. 4 b.y. ago. Degradation of the zircon structure, as reflected by the observed Raman spectral parameters, has occurred in this sample over a range of alpha-decay event dose from approx. 5.2 x 10(exp 14) to 1.4 x 10(exp 15) decay events per milligram of zircon, as calculated from the U and Th concentrations. This dose is well below the approx. 10(exp 16) events per milligram cumulative dose that causes complete metamictization and indicates that laser Raman microprobe spectroscopy is an analytical technique that is very sensitive to the radiation-induced damage in zircon.

Wopenka, Brigitte↗
DOE OSTI2023

Distribution of rare earth and other critical elements in lignites from the Eocene Jackson Group, Texas

Coal is increasingly evaluated as a source of rare earth elements (REEs) in the United States to address the overreliance on imported REEs. The objective of this study was to assess the distribution of REEs in lignites from selected mining areas in the Texas Gulf Coastal Plain region. Thirty-one archived lignite and rock samples previously collected by the U.S. Geological Survey were analyzed for their rare earth element and critical mineral content. These include samples from one core (5400 and 5500 lignite horizons) and two opencast lignite mines (Gibbons Creek 3500 and 4500 horizons, and San Miguel horizons A to D) in the Eocene Jackson Group of the Texas Gulf of Mexico Coastal Plain. Some lithologies in the Gibbons Creek 3500 and 4500 lignite-bearing sections have high total rare earth, yttrium (Y), and scandium (Sc) (REYSc) values, up to 7800 ppm (ash basis) REYSc. The lignite lithologies show an enrichment in rare earths, [samarium (Sm) through gadolinium (Gd)]. The basal Gibbons Creek 3500 lignite bench shows a heavy rare earth element enrichment pattern resembling that often seen in peats through high volatile A bituminous coals. The 5500 lignite sequence, overlying the latter lignite sections, shows a light rare earth enrichment. The San Miguel lignite benches have heavy rare earth enrichments with a negative europium (Eu) anomaly.

58 GEOSCIENCES↗
DOE OSTI2022

Production of Very Light Elements and Strontium in the Early Ejecta of Neutron Star Mergers

Abstract We study the production of very light elements ( Z < 20) in the dynamical and spiral-wave wind ejecta of binary neutron star mergers by combining detailed nucleosynthesis calculations with the outcome of numerical relativity merger simulations. All our models are targeted to GW170817 and include neutrino radiation. We explore different finite-temperature, composition-dependent nuclear equations of state, and binary mass ratios, and find that hydrogen and helium are the most abundant light elements. For both elements, the decay of free neutrons is the driving nuclear reaction. In particular, ∼0.5–2 × 10 −6 M ⊙ of hydrogen are produced in the fast expanding tail of the dynamical ejecta, while ∼1.5–11 × 10 −6 M ⊙ of helium are synthesized in the bulk of the dynamical ejecta, usually in association with heavy r -process elements. By computing synthetic spectra, we find that the possibility of detecting hydrogen and helium features in kilonova spectra is very unlikely for fiducial masses and luminosities, even when including nonlocal thermodynamic equilibrium effects. The latter could be crucial to observe helium lines a few days after merger for faint kilonovae or for luminous kilonovae ejecting large masses of helium. Finally, we compute the amount of strontium synthesized in the dynamical and spiral-wave wind ejecta, and find that it is consistent with (or even larger than, in the case of a long-lived remnant) the one required to explain early spectral features in the kilonova of GW170817.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2022

Digestion processes and elemental analysis of oxide and sulfide solid electrolytes

Detailed elemental analysis is essential for a successful development and optimization of material systems and synthesis methods. This is especially relevant for Li- and Na-containing compounds, found in state-of-the-art and next-generation battery systems. Their materials’ properties and thus the final device performance strongly depend on the crystal structure, the stoichiometry, and defect chemistry, e.g., influencing charge carrier concentration and activation energies for vacancy transport. However, a detailed quantitative analysis of light elements in a heavy matrix, featuring a broad range of solubilities and vapor pressures, is often difficult and associated with large uncertainties and thus neglected in favor of just reporting the stoichiometry as “weighed in.” Here, in this work, we report several approaches to digest and dissolve various oxide and sulfide-based materials, used in next-generation Li batteries, for elemental analysis via optical emission spectroscopy. These include the most common solid electrolytes Li-La-Ti–O, a perovskite material (LLTO), and Li-La-Zr-O which has garnet structure (LLZO). Additionally, a facile thermal digestion process is reported for a surrogate sulfide solid electrolyte (Na 2 S). The digestion procedures reported here are suitable for almost any laboratory environment and, when applied, will improve understanding of the synthesis-structure–property correlations needed to advanced batteries with all solid-state configurations.

Malkowski, Thomas F.↗
DOE OSTI2021

Distribution of rare earth elements in the pilot-scale processing of fly ashes derived from eastern Kentucky coals: Comparisons of the feed and processed ashes

Beneficiated fly ash from the combustion of Central Appalachian high volatile bituminous coals was extracted with HNO 3 in a pilot-scale processing plant. Several major oxides (notably CaO and SO 3 , but also including Fe 2 O 3 , MgO, K 2 O, and P 2 O 5 ) and minor elements (Mn, As, Sr, Ba, and Pb) are depleted in the post-HNO 3 -extraction spent ash. The total lanthanides, Y, and Sc concentration is reduced by about 20% in the spent ash, with Gd showing the greatest decrease. Along with Gd, Nd and Dy are also well differentiated between the feed and spent ashes, with La and Sm showing minimal partitioning. The Gd decrease is correlated with the depletion of Fe 2 O 3 . The heavy rare earth elements (REE heavier than Eu) and Y are disproportionately concentrated in the HNO 3 -leachate compared to the light REE. For the ashes studied, Sc did not partition between the feed and spent ashes. Pozzolanicity tests show that the compressive strength and strength activity indices of the spent ash + ordinary Portland cement (OPC) mixes are comparable to 100% OPC, indicating that the spent ashes produced in the pilot-scale runs have the potential to be sold as a Class F fly ash. Finally, the beneficiated ash chemistry influences the chemistry of the post-HNO 3 -extraction spent ash and the HNO 3 -leachate. A 500-ppm-REE fly ash will presumably be a more economically favorable feedstock than an ash with a significantly lesser concentration.

01 COAL, LIGNITE, AND PEAT↗
NASA NTRS1994

Compositional Variation in Apollo 16 Impact-Melt Breccias and Inferences for the Geology and Bombardment History of the Central Highlands of the Moon

High-precision data for the concentrations of a number of lithophile and siderophile elements were obtained on multiple subsamples from 109 impact-melt rocks and breccias (mostly crystalline) from the Apollo 16 site. Compositions of nearly all Apollo 16 melt rocks fall on one of two trends of increasing Sm concentration with increasing Sc concentration. The Eastern trend (lower Sm/Sc, Mg/Fe, and Sm/Yb ratios) consists of compositional groups 3 and 4 of previous classification schemes. These melt rocks are feldspathic, poor in incompatible and siderophile elements, and appear to have provenance in the Descartes formation to the east of the site. The Western trend (higher Sm/Sc. Mg/Fe, and Sm/ Yb ratios) consists of compositional groups 1 and 2. These relatively mafic, KREEP-bearing breccias are a major component (approx.35%) of the Cayley plains west of the site and are unusual, compared to otherwise similar melt breccias from other sites, in having high concentrations of Fe-Ni metal ( 1-2 %). The metal is the carrier of the low-Ir/Au (approx. 0.3 x chondritic) siderophile-element signature that is characteristic of the Apollo 16 site. Four compositionally distinct groups (1M, 1F, 2DB, and 2NR) of Western-trend melt breccias occur that are each represented by at least six samples. Compositional group 1 or previous classification schemes (the 'poikilitic' or 'LKFM' melt breccias) can be subdivided into two groups. Group 1M (represented by six samples, including 60315) is characterized by lower Al2O3 concentrations, higher MgO and alkali concentrations, and higher Mg/Fe and Cr/Sc ratios than group 1F (represented by fifteen samples, including 65015). Group 1M also has siderophile-element concentrations averaging about twice those of group lF and Ir/Au and Ir/Ni ratios that are even lower than those of other Western-trend melt rocks (Ir/Au = 0.24 +/- 0.03. CI-normalized). At the mafic extreme of group 2 ('VHA' melt breccias), the melt lithology occurring as clasts in feldspathic fragmental breccias from North Ray crater (group 2NR) is compositionally distinct from the melt lithology ofdimict breccias from the Cayley plains (group 2DB) in having higher concentrations of Sc, Cr, and heavy rare earth elements and lower concentrations of siderophile elements. The distinct siderophile-element signature (high absolute abundances, low Ir/Au ratio) suggest that the four groups ofmafic melt breccia are all somehow related. Ratios ofsome lithophile elements also suggest that they are more closely related to each other than then, are to melt breccias from other Apoll sites. However, none of the breccia compositions can be related to any of the others by any simple process of igneous fractionation or mixing involving common lunar materials. Thus, the origin of the four groups of mafic melt breccia is enigmatic. If they were produced in only one or two impacts, then a mechanism exists for generating regimes of impact-melt breccia in a single impact that are substantially different from each other in composition. For various reasons, including the problem of delivering large volumes of four different types of melt to the Apollo 16 site, it is unlikely that any of these breccias were produced in basin-forming impacts. If they were produced in as many as four crater-forming impacts, then the unusual siderophile-element signature is difficult to explain. Possible explanations are (1) the four groups of melt breccia all contain metal from a single, earlier impact, (2) they were each formed by related metal-rich meteoroids, or (3) some common postimpact process has resulted in metal of similar composition in each of four melt pools. Within a compositional group, most intrasample and intersample variation in lithophile element concentrations is caused by differences among samples in the proportion of a component of normative anorthosite or noritic anorthosite. In most cases, this compositional variation probably reflects variation in clast abundance. For group 2DB (and probably 2NR), differences in abundance of a component of ferroan anorthosite (estimated Al2O3 approx. 32%) accounts for the compositional variation. For groups 1M and 1F, the anorthositic component is more mafic (estimated Al203 approx. 26%). Some group-2 samples may be related by a troctolitic component of varying abundance.

Korotev, Randy L.↗
DOE OSTI2026

Low-energy measurement of the 25 Mg ⁢(𝛼,𝑛)⁢ 28 Si reaction via neutron spectroscopy

During core helium and carbon burning in massive stars, neutrons are produced mainly by the 22 Ne⁢ (𝛼,𝑛) ⁢25 Mg reaction. Some of these released neutrons are captured by heavy seed nuclei from previous nucleosynthesis events, resulting in the slow production of many of the elements between masses 60 ≤ 𝐴 ≤ 90 via the weak 𝑠 process. Determining the overall neutron flux available in this environment is one of the main challenges in modeling its contributions to heavy element production. Not only must the reaction rate be well defined for the primary neutron source, but the rates of neutron poison and recycling reactions must also be well determined. One critical reaction in the simulation network is 25 Mg ⁢(𝛼,𝑛) ⁢ 28 Si. This reaction, together with 25 Mg ⁢(𝑛,𝛾)⁢ 26 Mg and 25 Mg⁢ (𝛼,𝛾) ⁢ 29 Si, determine how 25 Mg nuclei affect the available neutron flux. Past attempts to measure the 25 Mg ⁢(𝛼,𝑛)⁢ 28 Si cross section using neutron moderator counters have been greatly hindered by lower-𝑍 background reactions. Here, in the present work, neutron spectroscopy with deuterated liquid scintillator detectors has been used. The experimental spectra have been analyzed by applying spectrum unfolding techniques to achieve improved background discrimination for the 25 Mg⁢ (𝛼,𝑛)⁢ 28 Si reaction at low energies, down to 𝐸 𝛼 = 1.75 MeV. The separation of the different background contributions gives further insight into the results of previous moderator counter measurements and the measurements lead to a revised and more reliable determination of the reaction rate.

hydrostatic stellar nucleosynthesis↗
DOE OSTI2024

Advances in heavy alkaline earth chemistry provide insight into complexation of weakly polarizing Ra 2+ , Ba 2+ , and Sr 2+ cations

Numerous technologies—with catalytic, therapeutic, and diagnostic applications—would benefit from improved chelation strategies for heavy alkaline earth elements: Ra 2+ , Ba 2+ , and Sr 2+ . Unfortunately, chelating these metals is challenging because of their large size and weak polarizing power. We found 18-crown-6-tetracarboxylic acid (H 4 COCO) bound Ra 2+ , Ba 2+ , and Sr 2+ to form M(H x COCO) x–2 . Upon isolating radioactive 223 Ra from its parent radionuclides ( 227 Ac and 227 Th), 223 Ra 2+ reacted with the fully deprotonated COCO 4- chelator to generate Ra(COCO) 2- (aq) (log K Ra(COCO)2- = 5.97 ± 0.01), a rare example of a molecular radium complex. Comparative analyses with Sr 2+ and Ba 2+ congeners informed on what attributes engendered success in heavy alkaline earth complexation. Chelators with high negative charge [-4 for Ra(COCO) 2- (aq) ] and many donor atoms [≥11 in Ra(COCO) 2- (aq) ] provided a framework for stable complex formation. These conditions achieved steric saturation and overcame the weak polarization powers associated with these large dicationic metals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Removal of Iron from Pyrite-Rich Coal Refuse by Calcination and Magnetic Separation for Hydrometallurgical Extraction of Rare Earth Elements

In the metallurgical extraction of rare earth elements (REEs), the ratio of contaminant ions to REEs in the leachate dictates the cost and operational efficiency of the downstream processes. The current study investigated the potential iron contamination removal from the feed to the hydrometallurgical process by calcination followed by magnetic separation. The 2.20 specific gravity sink fraction of Baker coal seam coarse refuse was pulverized to finer than 180 μm, calcined at various temperatures, and separated into magnetic and non-magnetic fractions using a wet high-intensity magnetic separator at different field strengths. The untreated feed, calcined products, and their subsequent magnetic and non-magnetic fractions were subjected to acid leaching tests with 1.2 M sulfuric acid at 75 °C and 1% w/v solids concentration. The recovery of light and heavy rare earth elements (LREEs and HREEs, respectively) along with the concentration of common contaminant ions (Al, Ca, and Fe) were measured as output variables. The weight percent of magnetic material was maximized at approximately 29% by calcination at a temperature of 400 °C. Magnetic removal of this fraction using a field strength of 1.15 Tesla resulted in the rejection of 81% of the iron. Leaching of the magnetic fraction provided significantly higher Fe recovery relative to untreated feed material and the non-magnetic fraction. The non-magnetic fraction was subsequently calcined at 600 °C to dehydroxylate the clays and released the REE minerals in the same manner as the treatment of the original coarse refuse material. A comparison of the leachate elemental concentrations resulting from the leaching of both the calcined non-magnetic and original coarse refuse showed only a slight reduction in the iron content from the non-magnetic material. This finding combined with the REE loss in the magnetic fraction resulted in the conclusion that the magnetic removal step was unfavorable.

58 GEOSCIENCES↗
DOE OSTI2023

Ultra-low concentration terbium (Tb) adsorption on garlic peels biosorbent and its application for $\mathrm{Nd}$-$\mathrm{Fe}$-$\mathrm{B}$ scraps recovery

Motivated by the strategic value of middle-heavy rare earth elements (MHREEs), we proposed a bio-adsorption method to recover ultra-low concentration terbium (Tb(Ⅲ)) from industrial wastewater that originated from the Nd-Fe-B scraps recovery process. It could be found that Tb(Ⅲ) ions as low as 5.34 ng·mL -1 (ppb) could be adsorbed onto Ca(Ⅱ)-modified garlic peels (Ca-GP) within 10 min with the adsorption efficiency of 99.2% at pH 3.5. The adsorption behavior of Tb(Ⅲ) onto Ca-GP conformed the Langmuir isotherm model and pseudo-second-order kinetic model. Attenuated total reflection Fourier Transform Infrared Spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS) and density-functional theory (DFT) calculations results showed that Tb(Ⅲ) ions could be ion-exchanged with cations in Ca-GP such as Ca(Ⅱ) and -COOH. In application, column experiment results showed that the maximum bed adsorption capacity for Tb, praseodymium (Pr), neodymium (Nd), dysprosium (Dy), and Total rare earth elements (REEs) ions calculated by the Thomas model was 0.06, 3.50, 9.65, 7.34, and 27.37 µg·g -1 , respectively, with the initial concentration of 0.37 ng·mL -1 Tb, 20 ng·mL -1 Pr, 44 ng·mL -1 Nd, 67 ng·mL -1 Dy and 170 ng·mL -1 total REEs ions of actual solutions (below the solubility of rare-earth hydroxide). Here this manuscript thus provided a novel cost-effective and efficient approach to the enrichment and recovery of MHREEs from ultra-low concentration REEs ions-containing solutions.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Machine learning molecular dynamics simulations toward exploration of high-temperature properties of nuclear fuel materials: case study of thorium dioxide

Predicting materials properties of nuclear fuel compounds is a challenging task in materials science. Their thermodynamical behaviors around and above the operational temperature are essential for the design of nuclear reactors. However, they are not easy to measure, because the target temperature range is too high to perform various standard experiments safely and accurately. Moreover, theoretical methods such as first-principles calculations also suffer from the computational limitations in calculating thermodynamical properties due to their high calculation-costs and complicated electronic structures stemming from f-orbital occupations of valence electrons in actinide elements. Here, we demonstrate, for the first time, machine-learning molecular-dynamics to theoretically explore high-temperature thermodynamical properties of a nuclear fuel material, thorium dioxide. The target compound satisfies first-principles calculation accuracy because f-electron occupation coincidentally diminishes and the scheme meets sampling sufficiency because it works at the computational cost of classical molecular-dynamics levels. We prepare a set of training data using first-principles molecular dynamics with small number of atoms, which cannot directly evaluate thermodynamical properties but captures essential atomistic dynamics at the high temperature range. Then, we construct a machine-learning molecular-dynamics potential and carry out large-scale molecular-dynamics calculations. Consequently, we successfully access two kinds of thermodynamic phase transitions, namely the melting and the anomalous λ transition induced by large diffusions of oxygen atoms. Furthermore, we quantitatively reproduce various experimental data in the best agreement manner by selecting a density functional scheme known as SCAN. Our results suggest that the present scale-up simulation-scheme using machine-learning techniques opens up a new pathway on theoretical studies of not only nuclear fuel compounds, but also a variety of similar materials that contain both heavy and light elements, like thorium dioxide.

74 ATOMIC AND MOLECULAR PHYSICS↗