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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
NASA NTRS1997

Efficient algorithms for robust feature matching

One of the basic building blocks in any point-based registration scheme involves matching feature points that are extracted from the sensed image to their counterparts in the reference image. This leads to the fundamental problem of point matching: given two sets of points, find the affine transformation that transforms one point set so that its distance from the other point set is minimized. Because of measurement errors and the presence of outlying data points, it is important that the distance measure between two point sets be robust to these effects. We measure distances using the generalized Hausdorff distance. Point matching can be a computationally intensive task, and there have been a number of algorithms and approaches proposed for solving this problem both theoretical and applied. We present two approaches to the point matching problem, in an attempt to reduce the computational complexity of the problem, while still providing guarantees on the quality of the final match. Our first method is an approximation algorithm, which is loosely based on a branch-and-bound approach due to Huttenlocher and Rucklidge. We show that by varying the approximation error bounds, it is possible to achieve a tradeoff between the quality of the match and the running time of the algorithm. Our second method involves a Monte Carlo method for accelerating the search process used in the first algorithm. With high probability this method succeeds in finding an approximately optimal match. We establish the efficiency of our approaches empirically.

Mount, David M.↗
DOE OSTI2025

Investigation of the Effect of Framework Flexibility on CO 2 Adsorption in SIFSIX-3-Cu Using a Machine-Learned Force Field

Metal–organic frameworks (MOFs) offer promise as selective CO 2 sorbents, but successful MOF sorbent materials need high CO 2 binding affinity and selectivity for CO 2 over water. This work focuses on the use of machine-learned force fields (MLFFs) to model CO 2 adsorption in flexible MOFs, with a focus on SIFSIX-3-Cu, an anion-pillared MOF known for its high CO 2 affinity. A preliminary high-throughput screening of over 900 anion-pillared MOFs was performed using rigid UFF+DDEC6 force fields to predict zero-loading heats of adsorption for CO 2 and H 2 O. SIFSIX-3-Cu was selected for further computational study due to its predicted CO 2 heat of adsorption and experimental relevance. A DeePMD-based MLFF was trained to reproduce DFT (PBE+D3) energies and forces, with an iterative sampling scheme combining molecular dynamics, geometry optimization, random geometric insertion, and NVT Monte Carlo-based configuration generation to capture both attractive and repulsive regions of the potential energy surface. Flexibility of the MOF was explicitly included, contrasting with previous models that approximated the MOF as rigid. Hybrid Monte Carlo/molecular dynamics (MC/MD) simulations with the MLFF produced CO 2 adsorption isotherms in good agreement with experimental data at direct air capture (DAC) pressures (e.g., 40 Pa), in contrast to previous overestimations of CO 2 sorption by models with rigid structures. Bond and angle histogram analysis showed that MOF flexibility increased the variance of fluorine–fluorine diagonal distances at adsorption sites, resulting in a lower predicted sorption for flexible, asymmetric SIFSIX-3-Cu pore geometries compared to the rigid, symmetric DFT-optimized SIFSIX-3-Cu pore geometry. A detailed description of flexibility afforded by the MLFF resulted in an accurately predicted CO 2 uptake (0.88 mmol/g) at low pressure (40 Pa) compared to the experimentally measured value (1.24 mmol/g). In conclusion, these results underscore the importance of including framework flexibility when modeling adsorption phenomena in MOFs, particularly for low-pressure applications.

adsorption↗
DOE OSTI2023

Prediction of the structures and heats of formation of MO 2 , MO 3 , and M 2 O 5 for M = V, Nb, Ta, Pa

Structures for the mono-, di-, and tri-bridge isomers of M 2 O 5 as well as those for the MO 2 and MO 3 fragments for M = V, Nb, Ta, and Pa were optimized at the density functional theory (DFT) level. Single point CCSD(T) calculations extrapolated to the complete basis set (CBS) limit at the DFT geometries were used to predict the energetics. Here, the lowest energy dimer isomer was the di-bridge for M = V and Nb and the tri-bridge for M = Ta and Pa. The di-bridge isomers were predicted to be composed of MO 2 + and MO 3 - fragments, whereas the mono- and tri-bridge are two MO 2 + fragments linked by an O 2 - . The heats of formation of M 2 O 5 dimers, as well as MO 2 and MO 3 neutral and ionic species were predicted using the Feller–Peterson–Dixon (FPD) approach. The heats of formation of the MF 5 species were calculated to provide additional benchmarks. Dimerization energies to form the M 2 O 5 dimers are predicted to become more negative going down group 5 and range from -29 to -45 kcal mol -1 . The ionization energies (IEs) for VO 2 and TaO 2 are essentially the same at 8.75 eV whereas the IEs for NbO 2 and PaO 2 are 8.10 and 6.25 eV, respectively. The predicted adiabatic electron affinities (AEAs) range from 3.75 eV to 4.45 eV for the MO 3 species and vertical detachment energies from 4.21 to 4.59 eV for MO 3 - . The calculated M[double bond, length as m-dash]O bond dissociation energies increase from 143 kcal mol -1 for M = V to ~170 kcal mol -1 for M = Nb and Ta to ~200 kcal mol -1 for M = Pa. The M–O bond dissociation energies are all similar ranging from 97 to 107 kcal mol -1 . Natural bond analysis provided insights into the types of chemical bonds in terms of their ionic character. Pa 2 O 5 is predicted to behave like an actinyl species dominated by the interactions of approximately linear PaO 2 + groups.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1998

Polymerization on the rocks: theoretical introduction

It is difficult if not impossible to synthesize long polymers of amino acids, nucleotides, etc., in homogeneous aqueous solution. We suggest that long polymers were synthesized on the surface of minerals in a prebiotic process analogous to solid-phase synthesis. Provided that the affinity of a mineral for an oligomer increases with the length of the oligomer, adsorption must become essentially irreversible for sufficiently long oligomers. Irreversibly adsorbed oligomers may be elongated indefinitely by repeated cycles in which the mineral with its adsorbed oligomers is first incubated with activated monomers and then washed free of deactivated monomer and side-products. We discuss in some detail the formation of oligomers of negatively-charged amino acids such as glutamic acid on anion-exchange minerals such as hydroxylapatite or illite. We show that the average length of adsorbed oligomers at steady state, n, depends on the balance between the rate of chain elongation and the rate of hydrolysis, and we derive a very approximate formula for n.

NASA Discipline Exobiology↗
NASA NTRS2000

Carbon isotopic composition of individual Precambrian microfossils

Ion microprobe measurements of carbon isotope ratios were made in 30 specimens representing six fossil genera of microorganisms petrified in stromatolitic chert from the approximately 850 Ma Bitter Springs Formation, Australia, and the approximately 2100 Ma Gunflint Formation, Canada. The delta 13C(PDB) values from individual microfossils of the Bitter Springs Formation ranged from -21.3 +/- 1.7% to -31.9 +/- 1.2% and the delta 13C(PDB) values from microfossils of the Gunflint Formation ranged from -32.4 +/- 0.7% to -45.4 +/- 1.2%. With the exception of two highly 13C-depleted Gunflint microfossils, the results generally yield values consistent with carbon fixation via either the Calvin cycle or the acetyl-CoA pathway. However, the isotopic results are not consistent with the degree of fractionation expected from either the 3-hydroxypropionate cycle or the reductive tricarboxylic acid cycle, suggesting that the microfossils studied did not use either of these pathways for carbon fixation. The morphologies of the microfossils suggest an affinity to the cyanobacteria, and our carbon isotopic data are consistent with this assignment.

Non-NASA Center↗
DOE OSTI2026

Diffusion and Solvation Dynamics of Ions in Water: Beyond the Brownian Approximation

The coupled dynamics of ions and water molecules in their first hydration shell impact a variety of processes including ion diffusion, selective ion transport in water-filled nanopores, and the kinetics of ion-pairing, ion adsorption, and metal-ligand binding reactions. In this work, we study these coupled dynamics for alkali metals (Li, Na, K, Rb, Cs), alkaline Earth metals (Mg, Ca, Sr, Ba), and chloride through the lens of their dependence on ion isotopic mass. Results are validated against previous measurements of the isotopic mass-dependence of ion diffusion coefficients in water and previous ab initio calculations of ion high-frequency dynamics in water. We find that the vibrational power spectra of ions in water consistently exhibit either two or three peaks, i.e., ions have several rattling frequencies within their solvations shells as previously reported for a subset of the species examined here. These frequencies have different sensititivies to isotopic mass that may serve as signatures of ion solvation processes (such as the tendency of ions to orient their first-shell water molecules) and that also may relate to Hofmeister-like effects including the relative affinity of different metals for ribonucleic acid (RNA).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1999

Collagenase-3 binds to a specific receptor and requires the low density lipoprotein receptor-related protein for internalization

We have previously identified a specific receptor for collagenase-3 that mediates the binding, internalization, and degradation of this ligand in UMR 106-01 rat osteoblastic osteosarcoma cells. In the present study, we show that collagenase-3 binding is calcium-dependent and occurs in a variety of cell types, including osteoblastic and fibroblastic cells. We also present evidence supporting a two-step mechanism of collagenase-3 binding and internalization involving both a specific collagenase-3 receptor and the low density lipoprotein receptor-related protein. Ligand blot analysis shows that (125)I-collagenase-3 binds specifically to two proteins ( approximately 170 kDa and approximately 600 kDa) present in UMR 106-01 cells. Western blotting identified the 600-kDa protein as the low density lipoprotein receptor-related protein. Our data suggest that the 170-kDa protein is a specific collagenase-3 receptor. Low density lipoprotein receptor-related protein-null mouse embryo fibroblasts bind but fail to internalize collagenase-3, whereas UMR 106-01 and wild-type mouse embryo fibroblasts bind and internalize collagenase-3. Internalization, but not binding, is inhibited by the 39-kDa receptor-associated protein. We conclude that the internalization of collagenase-3 requires the participation of the low density lipoprotein receptor-related protein and propose a model in which the cell surface interaction of this ligand requires a sequential contribution from two receptors, with the collagenase-3 receptor acting as a high affinity primary binding site and the low density lipoprotein receptor-related protein mediating internalization.

NASA Discipline Musculoskeletal↗
DOE OSTI2025

A Thorough Characterization of the Tellurocyanate Anion

Tellurocyanate, [TeCN] − , is the heaviest group 16 congener of the cyanate anion, [OCN] − . Due to the relative instability of the C─Te bond, tellurocyanate chemistry has seen only scarce attention. Here, we present the facile synthesis and thorough characterization of [K@crypt-222][TeCN]. The anion is essentially linear with interatomic distances C─N = 1.150(6)Å and C─Te = 2.051(4)Å, thus approximating a C≡N triple bond and for C─Te a bond order between 1 and 2. Fully 13 C and 15 N labeled [Te 13 C 15 N] − allowed for the extraction of chemical shifts and all possible coupling constants ( 13 C = 77.8 ppm, 15 N = 285.7 ppm, 125 Te = −566 ppm, 1 J 13C-15N = 8 Hz, 1 J 13C-125Te = 748 Hz, 2 J1 5N-125Te = 55 Hz), which were also determined independently by quantum chemical calculations. In the series [ChCN] − (Ch = O─Te), [TeCN] − shows the strongest spin-orbit coupling (SOC) induced heavy-atom effect on the light-atom shielding (SO-HALA-effect). In contrast, 15 N shifts are also well described without considering relativistic effects and/or SOC. Negative-ion photoelectron spectroscopy was used to extract the electron affinity (EA = 3.034 eV) and spin-orbit splitting (3807 cm −1 ) of [TeCN] • . These values continue the trends of falling EA and rising SOC in the series [ChCN] • .

Bonding analysis↗
DOE OSTI2025

Extending quantum-mechanical benchmark accuracy to biological ligand-pocket interactions

Predicting the binding affinity of ligands to protein pockets is key in the drug design pipeline. The flexibility of ligand-pocket motifs arises from a range of attractive and repulsive electronic interactions during binding. Accurately accounting for all interactions requires robust quantum-mechanical (QM) benchmarks, which are scarce for ligand-pocket systems. Additionally, disagreement between “gold standard” Coupled Cluster (CC) and Quantum Monte Carlo (QMC) methods casts doubt on many benchmarks for larger non-covalent systems. We introduce the “QUantum Interacting Dimer” (QUID) benchmark framework containing 170 non-covalent (non-)equilibrium systems modeling chemically and structurally diverse ligand-pocket motifs. Symmetry-adapted perturbation theory shows that QUID broadly covers non-covalent binding motifs and energetic contributions. Robust binding energies are obtained using complementary CC and QMC methods, achieving agreement of 0.5 kcal/mol. The benchmark data analysis reveals that several dispersion-inclusive density functional approximations provide accurate energy predictions, though their atomic van der Waals forces differ in magnitude and orientation. Contrarily, semiempirical methods and empirical force fields require improvements in capturing non-covalent interactions (NCIs) for out-of-equilibrium geometries. The wide span of NCIs, highly accurate interaction energies, and analysis of molecular properties take QUID beyond the “gold standard” for QM benchmarks of ligand-protein systems.

Puleva, Mirela [University of Luxembourg, Luxembou↗
DOE OSTI2020

BWR Spent Nuclear Fuel Acquisition and Testing to Support DOE-NE High Burnup Spent Fuel Data Project

The Office of Spent Fuel and Waste Disposition (SFWD) within the US Department of Energy (DOE) Office of Nuclear Energy (NE) established the Spent Fuel and Waste Science and Technology (SFWST) campaign to conduct research and development (R&D) activities related to the storage, transportation, and disposal of spent nuclear fuel (SNF) and high-level radioactive waste. The SFWST program was created within SFWD to address issues of extended or long-term SNF storage and transportation. Some near-term objectives of SFWST are to use a science-based, engineering-driven approach to: Support the enhancement of the technical bases to support the continued safe and secure dry storage of SNF for extended periods; Support the enhancement of the technical bases for retrieving SNF after extended dry storage; Support the enhancement of the technical bases for transporting high burnup (HBU) fuel and transporting low burnup fuel and HBU fuel after dry storage DOE-NE, in partnership with the Electric Power Research Institute, developed the High Burnup Spent Fuel Data Project to perform a large-scale demonstration and laboratory-scale testing of HBU pressurized water reactor (PWR) fuels (exceeding 45 gigawatt-days per metric ton of uranium [GWd/MTU]). Under this project, 25 sister rods—which are rods that have the same design, power histories, and other characteristics—were removed from assemblies at the North Anna Nuclear Power Station and sent to Oak Ridge National Laboratory (ORNL) in January 2016. ORNL performed detailed nondestructive examination (NDE) on all 25 rods. The NDE consisted of visual examinations, gamma and neutron scanning, profilometry and rod length measurements, and eddy current examinations. After completing the NDE, 10 of the sister rods were delivered to Pacific Northwest National Laboratory (PNNL) in a NAC International, Inc. legal-weight truck cask in September 2018 for destructive examination (DE). To date, SFWD work has focused on the PWR fuel that is part of the Sister Rod Test program. No boiling water reactor (BWR) fuel has been tested in the program, and the data needs that were identified for the PWR fuel have not been collected for BWR fuel. The goal to obtain six to nine BWR rods and test them at ORNL will support closing this important data gap. BWR fuel comprises approximately 56% of the total fuel assemblies currently in storage at nuclear power plants in the United States. BWR nuclear fuel and cladding designs and manufacturing are significantly different from PWRs. Differences include the following: BWR fuel pellets are larger than PWR pellets; Variations of Zircaloy-2 (including liners) are used instead of the Zircaloy-4 cladding materials used in PWRs; Clad manufacturing and stress-relief processes are different between PWRs and BWRs; The fuel rod dimensions are different because larger rod diameters and thicker cladding are used in BWRs; BWR fuel typically has lower internal rod pressures and sees vastly different operating conditions than PWR fuel (i.e., two-phase flow); BWR assemblies are “canned,” meaning each assembly is surrounded by a metal fuel channel; BWR cladding is often composed of an inner pure Zr liner that has widely different mechanical properties than the Zircaloy-2 alloy and exhibits a stronger affinity for hydrogen; The BWR SNF generally has more total hydrogen in the cladding/liner than typical PWR fuel; The construction of the PWR and BWR assemblies is vastly different; BWR rods are solidly attached to the assembly nozzles and experience a much different vibration and shock load than PWR rods, which are “floating” within a grid system attached to guide tubes, and the rods sit loosely on the bottom end plates. These numerous differences will affect the way the BWR SNF responds under dry storage preparation processes (e.g., vacuum drying) and during transportation. The results collected in the PWR experimental program must be compared with a subset of similar data collected on BWR SNF to establish a technical basis for whether the larger PWR database is sufficient to bound the BWR SNF end-of-life conditions as is currently assumed for several fuel/clad properties. Changes that occur in both fuel types at HBU could exacerbate any mechanical property differences. As the fuel burnup increases, several changes occur that might affect the performance of the fuel, cladding, and assembly hardware in storage and transportation. These changes include increased cladding corrosion layer thickness, increased cladding hydrogen content, increased cladding creep strains, increased fission gas release, and the formation of the HBU structure at the surface of the fuel pellets. The Nuclear Regulatory Commission (NRC) limits the current maximum rod-averaged burnup to 62 GWd/MTU due to these changes and the lack of data at higher burnups.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Rare Earth Element-Induced Condensation of the Block V of the Repeats-in-Toxin Domain from CyaA from Bordetella pertussis for Separations

Rare earth elements (REEs) are critical for the development of a range of new technologies. However, the current industrial separation processes of these metals from natural sources, recycled materials, and industrial effluents involve the large consumption of organic solvents, resulting in a sizable environmental footprint. We aim to exploit the high affinity of the block V peptide of the repeats-in-toxin (RTX) domain of the adenylate cyclase protein from Bordetella pertussis for the separation of REEs. This peptide selectively binds with lanthanide (Ln) cations and can undergo Ln-induced phase separation, which can be used in bioseparation processes. Here, we evaluated the self-assembling structures of complexes of the RTX domain peptide folded in the presence of Ln 3+ cations. Size distribution and surface potential measurements of complexes were taken to understand the Ln-induced changes in the complexed peptide. Transmission electron microscopy imaging was used to explore the structures of complexes, while anomalous small-angle X-ray scattering measurements were used to determine the distribution of Ln 3+ ions within the protein-based macrostructures. In the presence of excess Ln 3+ , we observed the formation of coral-like cylindrical structures comprised of Ln 3+ -RTX complexes, with approximately eight trivalent metals per peptide within the nanosized assemblies. These findings provide new insights into the structural organization of assembled RTX domains and their ability to coordinate with REEs, forming nanosized, metal-rich structures that naturally condense, providing a proof-of-concept for protein-based separation processes of these critical materials.

chemical structure↗
DOE OSTI2020

Improvements in the orbitalwise scaling down of Perdew–Zunger self-interaction correction in many-electron regions

The Perdew-Zunger (PZ) method offers a way to remove the self-interaction (SI) error from density functional approximations on an orbital by orbital basis. The PZ method provides significant improvements for the properties such as barrier heights or dissociation energies but results in over-correcting the properties well described by SI-uncorrected semi-local functional. One cure to rectify the over-correcting tendency is to scale down the magnitude of SI-correction of each orbital in the many electron region. We have implemented the orbitalwise scaled down SI-correction (OSIC) scheme of Vydrov et al. [J. Chem. Phys. 124, 094108 (2006)] using the Fermi-L owdin SI-correction method. After validating the OSIC implementation with previously reported OSICLSDA results, we examine its performance with the most successful non-empirical SCAN meta-GGA functional. Using different forms of scaling factors to identify one-electron regions, we assess the performance of OSIC-SCAN for a wide range of properties: total energies, ionization potentials and electron affinities for atoms, atomization energies, dissociation and reaction energies, and reaction barrier heights of molecules. Our results show that OSIC-SCAN provides superior results than the previously reported OSIC-LSDA, -PBE, and -TPSS results. Furthermore, we propose selective scaling of OSIC (SOSIC) to remove its major shortcoming that destroys the -1/r asymptotic behavior of the potentials. The SOSIC method gives the highest occupied orbital eigenvalues practically identical to those in PZSIC and unlike OSIC provides bound atomic anions even with larger powers of scaling factors. Furthermore, SOSIC compared to PZSIC or OSIC provides more balanced description of total energies and barrier heights.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Testing of Crystalline Silicotitanate to Support Tank-Side Cesium Removal System Operations - 20458

The direct feed of waste from the Hanford tank farms to the Low-Activity Waste Facility at the Hanford Waste Treatment and Immobilization Plant requires an intermediate treatment step that prepares the waste for vitrification. Washington River Protection Solutions (WRPS) selected a near-tank treatment system known as the Tank-Side Cesium Removal (TSCR) system to perform the required intermediate treatment functions. The approach in the TSCR system is to filter waste supernatant with a sintered metal dead-end filter and then use a series of ion exchange columns to remove cesium; this system has several similarities to the Tank Closure Cesium Removal system that has been deployed on the Savannah River Site. The ion exchange media proposed for use is crystalline silicotitanate (CST), which is a non-elutable media with a high affinity for cesium. Because the media is non-elutable, loaded columns will be blown down with compressed air, moved into interim storage, and replaced with new columns when cesium capacity is reached. The assumed extent and rate of drying that could be achieved in the TSCR column geometry lacked confirmation by experimental data. In addition, once the columns are loaded with cesium, they generate flammable gases (primarily hydrogen) via radiolysis acting on any resident liquids, i.e., moisture, remaining in the media bed. An assessment of available information on CST concluded that gas generation data that bounds expected operational conditions were needed to support the TSCR system safety basis and planned operations. Working with WRPS, Pacific Northwest National Laboratory (PNNL) designed and conducted testing with CST media to address the need for (a) representative in-column drying data, and (b) bounding flammable gas generation data. Drying testing was performed using a full-height column with a diameter of approximately 2 inches with injected air at temperatures of 18 deg. C and 30 deg. C. Gas generation testing was conducted in an engineered bunker that allowed simultaneous irradiation of up to eight samples at a time. These two experimental approaches used at PNNL for the CST testing are summarized and the major outcomes are presented. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
NASA NTRS1996

Promoter-dependent and -independent activation of insulin-like growth factor binding protein-5 gene expression by prostaglandin E2 in primary rat osteoblasts

Insulin-like growth factor (IGF) action is mediated by high affinity cell surface IGF receptors and modulated by a family of secreted IGF binding proteins (IGFBPs). IGFBP-5, the most conserved of six IGFBPs characterized to date, uniquely potentiates the anabolic actions of IGF-I for skeletal cells. In osteoblasts, IGFBP-5 production is stimulated by prostaglandin E2 (PGE2), a local factor that mediates certain effects induced by parathyroid hormone, cytokines such as interleukin-1 and transforming growth factor-beta, and mechanical strain. In this study, we show that transcriptional and post-transcriptional events initiated by PGE2 collaborate to enhance IGFBP-5 gene expression in primary fetal rat osteoblast cultures. PGE2 treatment stimulated up to a 7-fold rise in steady-state levels of IGFBP-5 mRNA throughout 32 h of incubation. Analysis of nascent IGFBP-5 mRNA suggested that PGE2 had only a modest stimulatory effect on IGFBP-5 gene transcription, and transient transfection studies with IGFBP-5 promoter-reporter genes confirmed that PGE2 enhanced promoter activity by approximately 2-fold. Similar stimulatory effects were seen with forskolin. A DNA fragment with only 51 base pairs of the 5'-flanking sequence retained hormonal responsiveness, which may be mediated by a binding site for transcription factor AP-2 located at positions -44 to -36 in the proximal IGFBP-5 promoter. Incubation of osteoblasts with the mRNA transcriptional inhibitor 5,6-dichloro-1-beta-D-ribofuranosylbenzimidazole demonstrated that PGE2 enhanced IGFBP-5 mRNA stability by 2-fold, increasing the t1/2 from 9 to 18 h. The effects of PGE2 on steady-state IGFBP-5 transcripts were abrogated by preincubating cells with cycloheximide, indicating that the effects of PGE2 on both gene transcription and mRNA stability required ongoing protein synthesis. Therefore, both promoter-dependent and -independent pathways converge to enhance IGFBP-5 gene expression in response to PGE2 in osteoblasts.

Non-NASA Center↗
DOE OSTI2020

Origin of tungsten and geochemical controls on its occurrence and mobilization in shallow sediments from Fallon, Nevada, USA

In this study, tungsten (W) occurrence and speciation was investigated in sediments collected from Fallon, Nevada where previous studies have linked elevated W levels in human body fluids to an unusual cluster of childhood leukemia cases. The speciation of sedimentary W was determined by μ-XRF mapping and μ-XANES. The W content of the analyzed surface sediments ranged between 81 and 25,908 mg/kg, which is significantly higher than the W content in deeper sediments which ranged from 37 to 373 mg/kg at 30 cm depth. The μ-XANES findings reveal that approximately 20–50% of the total W in the shallow sediment occurs in the metallic form (W 0 ); the rest occurs in the oxide form (W VI O 3 ). Because W 0 does not occur naturally, its elevated concentrations in surface sediments point toward a possible local anthropogenic origin. The oxidation of metallic W 0 with meteoric waters likely leads to the formation of W VI O 3 . The chief water-soluble W species was identified as WO 4 2– by chromatographic separation and speciation modeling. These results led us to postulate that W 0 particles from a currently unknown but local source(s) is (are) deposited onto the soils and/or surface sediments. The W 0 in interaction with meteoric water is oxidized to W VI O 3 , and as these sediment-water interactions progress, WO 4 2– is formed in the water at pH ~7. Under pH < 7, and sufficient W concentrations, tungstate tends to polymerize, and polymerized species are less likely to adsorb onto sediments. Polymerized species have lower affinity than monomers, which leads to enhanced mobility of W.

58 GEOSCIENCES↗
DOE OSTI2026

Redox Potentials for Hydrogen Species in Acetonitrile and Tetrahydrofuran

The properties of the fundamental hydrogen species, proton (H+), hydrogen atom (H•), and hydride anion (H-) are critical to a vast range of chemical processes, yet their thermodynamic properties in nonaqueous solvents are not well established. A hybrid supermolecule-continuum approach is used to predict the Gibbs free energies of solvation (?G°solv) and standard redox potentials (E°) for the 2H+/H2 and H•/H- couples in acetonitrile (MeCN) and tetrahydrofuran (THF) following the approach previously used for water. Gas phase geometry optimizations were done using density functional theory (DFT) with the ?B97XD functional, Møller-Plesset second-order perturbation theory (MP2) with augmented correlation-consistent basis sets and composite-correlated molecular orbital theory (G3MP2 and G3MP2B3). Additional single point calculations in gas phase were performed for H- affinity for MeCN and THF at the coupled cluster CCSD(T) level using MP2 geometries. Solvation was included using the self-consistent reaction field SMD model. For H+, the ?G°solv values are predicted to be -252.2 kcal/mol in MeCN and -261.0 kcal/mol in THF. The redox potentials for the 2H+/H2 couple are +0.49 V in MeCN and +0.11 V in THF relative to the aqueous SHE, consistent with the available experimental data. The ?G°solv for H- is predicted to be -80 kcal/mol in MeCN and -68 in THF, and for H•, ?G°solv is predicted to be -1.3 kcal/mol in THF and -2.0 kcal/mol in MeCN. These solvation energies yield respective calculated redox potentials for the H•/H- couple of -0.14 V in MeCN and -0.68 V in THF relative to the aqueous SHE. H2 solvation is slightly exergonic in MeCN (-3.3 kcal/mol) and near thermoneutral in THF (+1.3 kcal/mol). The pKa(H2) is predicted to be 45.4 in MeCN and 47.8 in THF. The proton-coupled electron transfer (PCET) accounting term CG was evaluated giving values on the ferrocene scale within approximately 2 kcal/mol of literature in both solvents. These results provide benchmarks for hydrogen redox chemistry in MeCN and THF and improve consistency across E°, ?G°solv, pKa, and CG. These results provide benchmarks for hydrogen redox chemistry in nonaqueous media challenging previous estimates based on indirect extrapolations and assumptions.

Duda, Damian P.↗
NASA NTRS2017

A New Type of Foreign Clast in A Polymict Ureilite: A CAI or AL-Rich Chondrule

Introduction: Polymict ureilites are breccias interpreted to represent regolith formed on a ureilitic asteroid [1-3]. They consist of approximately 90-95% clasts of various ureilite types (olivine-pyroxene rocks with Fo 75-95), a few % indigenous feldspathic clasts, and a few % foreign clasts [4-20]. The foreign clasts are diverse, including fragments of H, L, LL and R chondrites, angrites, other achondrites, and dark clasts similar to CC [6,7,9-19]. We report a new type of foreign clast in polymict ureilite DaG 999. Methods: Clast 8 in Dar al Gani (DaG) 999/1 (Museum fur Naturkunde) was discovered during a survey of feldspathic clasts in polymict ureilites [19,20]. It was studied by BEI, EMPA, and X-ray mapping on the JEOL 8530F electron microprobe at ARES, JSC. Petrography and Mineral Compositions: Clast 8 is sub-rounded to irregular in shape, approximately 85 micrometers in diameter, and consists of approximately 68% pyroxene and 32% mesostasis (by area). Part of the pyroxene (top half of clast in Fig. 1a and 2) shows a coarse dendritic morphology; the rest appears massive. Mesostasis may be glassy and contains fine needles/grains of pyroxene. The pyroxene has very high CaO (23.5 wt.%) and Al2O3 (19.7 wt.%), with the formula: (Ca(0.91)Mg(0.63)Fe(0.01)Al(sup VI) (0.38)Cr(0.01)Ti(0.05)1.99 Si2O6. The bulk mesostasis also has very high Al2O3 (approximately 26 wt.%). A bulk composition for the clast was obtained by combining modal abundances with phase compositions (Table 1, Fig. 3). Discussion: The pyroxene in clast 8 has a Ca-Al-(Ti)- rich (fassaitic) composition that is clearly distinct from compositions of pyroxenes in main group ureilites [22] or indigenous feldspathic clasts in polymict ureilites [4-8]. It also has significantly higher Al than fassaite in angrites (up to approximately 12 wt.% [23]), which occur as xenoliths in polymict ureilites. Ca-Al-Ti rich pyroxenes are most commonly found in CAIs, Al-rich chondrules and other types of refractory inclusions in chondrites [21,24-31]. However, the clast 8 pyroxene matches only the most Al-Ca-rich of these, e.g., pyroxenes in type B CAIs in CV3 chondrites [25,30,31], a pyroxene-hibonite spherule and a pyroxene-anorthitespinel fragment from unique CC Acfer 094 [29], and one Al-rich chondrule from Chainpur (LL3.4) [21]. The mineralogy of clast 8 is not consistent with the mineral assemblages of any of these objects (since it lacks hibonite, spinel and/or anorthite), which suggests that it is unrepresentatively sectioned or is a fragment of a more mineralogically diverse object. Its bulk composition (Table 1; Fig. 3) is similar to bulk compositions of some Al-rich chondrules, as well as those of Type C CAIs (which plot in the sp+An+L field in Fig. 3), although it is enriched in silica relative to type C CAIs [e.g., 31]. This suggests a more likely affinity to Al-rich chondrules, although most Al-rich chondrules have less Al-Ca-rich pyroxene [21,26,27]. These bulk compositional comparisons may not be definitive, however, if the clast is unrepresentatively sampled. One of eleven Al-rich chondrules from UOCs described by [21] has textural and compositional characteristics that make it a possible progenitor type for clast 8. This chondrule (Chainpur 1251-14-2) is anorthiteporphyritic, with an interstitial dendritic intergrowth of pyroxene (similar in composition to that in clast 8) and plagioclase [21]. Clast 8 is conceivably a fragment from the interstitial area of such an object. The occurrence of glassy mesostasis (in clast 8) rather than plagioclase may not be a significant difference; it could result from a difference only in cooling rate. Al-rich chondrules with glassy mesostasis are rare, and known occurrences are Ca-poor [26], unlike clast 8. Polymict ureilites are known to contain xenoliths of various chondrites (including OC, R and CC) as well as individual ferromagnesian and silica-pyroxene chondrules probably derived from OC or RC [6,9,15,16,18]. This is the first report of an individual chondritic refractory inclusion as a xenolith in a polymict ureilite. An RC-like sample from anomalous polymict ureilite Almahata Sitta contains CAIs, but they are spinel-rich and not similar to clast 8 [13,14]. Further studies of this clast (which, unfortunately, may not be possible), or the discovery of additional (more representative?) materials of this type would be needed to determine the exact nature of this xenolith and the type of chondrite from which it is derived.

Goodrich, C. A.↗
DOE OSTI2020

TCCR Operational Summary and Optimization for Tank 9 Processing - 20314

Savannah River Remediation (SRR) manages and operates the liquid waste facilities at Savannah River Site (SRS) for the Department of Energy (DOE). Stored liquid waste is a complex mixture of insoluble solids (sludge) and soluble salts in an alkaline solution. SRR has deployed the Tank Closure Cesium Removal (TCCR) system, a tank-side ion exchange process, to remove radioactive cesium from salt waste and enable onsite disposal of the resulting decontaminated salt solution as low-level waste at the Saltstone facilities. The TCCR system consists of two prefilters, four ion exchange (IX) columns, one resin trap, and a ventilation system. The IX process uses a form of inorganic crystalline silicotitanate (CST), which has a high affinity for cesium and other alkali metals, strontium, and actinides. This process is currently deployed utilizing salt feed from Tank 10, with future plans to dissolve solid salt in Tank 9 and transfer the salt solution to Tank 10 for processing through TCCR. The feed for TCCR must be created from salt-cake in Tank 10 through a dissolution process. Once enough salt has been dissolved, a qualification process is entered. This process characterizes the feed and ensures the cesium loading on the columns will not cause boiling of waste within the columns during or after processing. Once the batch has been qualified, salt waste is fed to the TCCR system through a transfer pump in the center of the tank. The waste is filtered through a set of two shielded, dead-end prefilters that prevent solids buildup in the columns. The filtered salt solution then travels to the shielded IX columns, which can be operated individually or in series, where the cesium is sorbed on the CST media. The decontaminated salt solution (DSS) then travels through a resin trap and out of the module to Tank 11. TCCR has successfully processed approximately 795,000 L of Tank 10H radioactive salt waste over two batches to date. There has not yet been a system induced shutdown. The prefilters performed as expected with only minor degradation in recovery of differential pressure after a backflush sequence. The time between backflushes decreased as each batch reached the end of processing. The hydraulics in the IXCs mostly performed as expected at all flow rates, except for one IXC that will be further investigated during Batch 3 processing. The TCCR system has shown some opportunities for more efficient processing during the length of the demonstration so far. For future processing of material from Tank 9H through Tank 10H and the TCCR unit, TCCR 1A will implement changes to the prefilters and the IXCs. The prefilters will have an increased surface area and a new filter media in an effort to increase time between filter swaps and improve backwashing cleaning capability. The IXCs will have a reduced diameter to allow for increased heat transfer out of the column and increased loading of Cs-137. Additionally, a new form of CST with an increased kinetic performance is being investigated for use during TCCR 1A operation. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗