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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Identification of uranium oxidation states using oxygen K-edge scanning transmission X-ray microscopy

The field of nuclear forensics is growing in importance, and the increasing capabilities at synchrotron radiation light sources enable non-destructive characterization of oxide particles with better spatial, compositional, and oxidation state speciation resolution than ever before. Here, uranium oxide particles derived from multiple wet chemical processing methods were examined using a scanning transmission X-ray microscope (STXM), and a weakly-supervised method was developed to automatically analyze the collected data. Multiple uranium oxidation states were observed and quantified within and between samples, yielding information about differences between particles produced via the various processing routes.

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

Prediction of Redox Potentials for Different Oxidation States of U, Np, Pu, and Am in Alkaline Aqueous Solution

The redox potentials for U, Np, Pu, and Am for oxidation states +III up to +VIII in alkaline aqueous solutions were predicted using density functional theory (DFT) and small-core pseudopotentials and their basis sets, with a hybrid explicit/implicit solvent model using SHE = 4.28 V. For each oxidation state, various oxo/hydroxo complexes were evaluated resulting in a variety of one-electron redox pathways. For An(VIII/VII) couples, the predicted redox potentials for the [An(VIII)O 5 (OH)] -3 /[An(VII)O 4 (OH) 2 ] -3 , or [An(VIII)O 4 (OH) 2 ] -2 /[An(VII)O 4 (OH) 2 ] -3 couples are in good agreement with existing estimates. For An(VII/VI) redox couples, all couples, particularly [An(VII)O 4 (OH) 2 ] -3 /[An(VI)O 2 (OH) 4 ] -2 , were in agreement with experimental values for U, Np, and Pu, but the results for Am showed larger differences from the estimated potentials. The An(VI/V) couples were consistent with experiment for dioxo/tetrahydroxo couples, and the An(V/IV) couples showed acceptable agreement based on actinide-specific couples, with neutral hydroxides often favored in the +IV state. The An(IV/III) couples were consistent with literature values when modeled as soluble neutral hydroxides. The use of our approach yielded calculated redox potentials that were within ±0.2 V from experimental or estimated values consistent with our prior calculations on redox potentials of actinides from Ac to Am in acidic aqueous solutions. Finally, as a result, this supports the robustness of our DFT-based methodology for predicting actinide redox potentials, offering valuable insights for actinide chemistry in aqueous solutions.

Actinides↗
NASA NTRS1985

Oxidation states of iron in the terrestrial planets: Evidence and implications for accretion models

Analyses of Mars spectra reveal that primary minerals may be more iron rich than average basalts on Earth, and the oxidation state of iron in the pyroxines suggests equally high or higher oxygen fugacities on Mars than Earth. Analysis of Mercury spectra reveal that silicate iron contents are substantially lower than those on Mars. Mercury, however, probably has a substantial iron core. This is consistent with a lower oxidation state of iron on Mercury than on Mars. These findings are consistent with predictions of models of equilibrium condensation and homogeneous accretion. Those models predict that Mercury would have negligible Fe(2+) in silicates (Fe/Fe+Mg approx. 0.5). For Mercury iron should be virtually all metallic, while for Mars the iron would be all oxidized as FeS and silicate. Surface measurements of Fe/Fe+Mg on Venus, Earth, and Mars further support the predicted relative increase in Fe/Fe+Mg ratio (increased oxidation state) with distance from the Sun. The implied high oxygen fugacities on Mars (Fe(3+) in silicates) provide additional consistence with the model predictions.

Huguenin, R. L.↗
DOE OSTI2024

Prediction of the Cu oxidation state from EELS and XAS spectra using supervised machine learning

Abstract Electron energy loss spectroscopy (EELS) and X-ray absorption spectroscopy (XAS) provide detailed information about bonding, distributions and locations of atoms, and their coordination numbers and oxidation states. However, analysis of XAS/EELS data often relies on matching an unknown experimental sample to a series of simulated or experimental standard samples. This limits analysis throughput and the ability to extract quantitative information from a sample. In this work, we have trained a random forest model capable of predicting the oxidation state of copper based on its L-edge spectrum. Our model attains an R 2 score of 0.85 and a root mean square error of 0.24 on simulated data. It has also successfully predicted experimental L-edge EELS spectra taken in this work and XAS spectra extracted from the literature. We further demonstrate the utility of this model by predicting simulated and experimental spectra of mixed valence samples generated by this work. This model can be integrated into a real-time EELS/XAS analysis pipeline on mixtures of copper-containing materials of unknown composition and oxidation state. By expanding the training data, this methodology can be extended to data-driven spectral analysis of a broad range of materials.

36 MATERIALS SCIENCE↗
NASA NTRS2015

Evolution of the Oxidation State of the Earth's Mantle

The oxidation state of the Earth's mantle during formation remains an unresolved question, whether it was constant throughout planetary accretion, transitioned from reduced to oxidized, or from oxidized to reduced. We investigate the stability of Fe3(+) at depth, in order to constrain processes (water, late accretion, dissociation of FeO) which may reduce or oxidize the Earth's mantle. In our previous experiments on shergottite compositions, variable fO2, T, and P less than 4 GPa, Fe3(+)/sigma Fe decreased slightly with increasing P, similar to terrestrial basalt. For oxidizing experiments less than 7GPa, Fe3(+)/sigma Fe decreased as well, but it's unclear from previous modelling whether the deeper mantle could retain significant Fe3(+). Our current experiments expand our pressure range deeper into the Earth's mantle and focus on compositions and conditions relevant to the early Earth. Preliminary multi-anvil experiments with Knippa basalt as the starting composition were conducted at 5-7 GPa and 1800 C, using a molybdenum capsule to set the fO2 near IW, by buffering with Mo-MoO3. TEM and EELS analyses revealed the run products quenched to polycrystalline phases, with the major phase pyroxene containing approximately equal to Fe3(+)/2(+). Experiments are underway to produce glassy samples that can be measured by EELS and XANES, and are conducted at higher pressures.

Danielson, L. R.↗
NASA NTRS2017

Mapping the Iron Oxidation State in Martian Meteorites

Several types of Martian igneous meteorites have been identified: clinopyroxenites (nakhlites), basaltic shergottites, peridotitic shergottites, dunites (chassignites) and orthopyroxenites [1,2]. In order to constrain the heterogeneity of the Martian mantle and crust, and their evolution through time, numerous studies have been performed on the iron oxidation state of these meteorites [3,4,5,6,7,8,9]. The calculated fO2 values all lie within the FMQ-5 to FMQ+0.5 range (FMQ representing the Fayalite = Magnetite + Quartz buffer); however, discrepancies appear between the various studies, which are either attributed to the choice of the minerals/melts used, or to the precision of the analytical/calculation method. The redox record in volcanic samples is primarily related to the oxidation state in the mantle source(s). However, it is also influenced by several deep processes: melting, crystallization, magma mixing [10], assimilation and degassing [11]. In addition, the oxidation state in Martian meteorites is potentially affected by several surface processes: assimilation of sediment/ crust during lava flowing at Mars' surface, low temperature micro-crystallization [10], weathering at the surface of Mars and low temperature reequilibration, impact processes (i.e. high pressure phase transitions, mechanical mixing, shock degassing and melting), space weathering, and weathering on Earth (at atmospheric conditions different from Mars). Decoding the redox record of Martian meteorites, therefore, requires large-scale quantitative analysis methods, as well as a perfect understanding of oxidation processes.

Martin, A. M.↗
DOE OSTI2025

Quantification of Oxygen Vacancies in SrFe0.5Cr0.5O3−δ Thin Films: Correlating Lattice Expansion with Oxidation State Variability

Oxygen vacancies (VO), even in the dilute regime, can significantly impact the physical and chemical properties of complex oxides. It is however challenging to reliably detect and adequately quantify such defects in thin film samples where the VO concentration and distribution may further vary in response to interfacial strain. Here, we present a method to quantify VO concentrations in SrFe0.5Cr0.5O3−δ (SFCO) epitaxial thin films. Through coherent Bragg rod analysis, X-ray absorption spectroscopy, and theoretical modeling, we systematically correlate the c-axis lattice expansion detected in SFCO films with a VO concentration gradient. Our results reveal a nearly linear relationship between oxygen off-stoichiometry and out-of-plane lattice expansion in coherently strained SFCO films, with δ increasing from 0.32 to 0.52 and the lattice expanding by ∼1.0%. Moreover, a significant decrease in Cr oxidation state (from Cr5+ to Cr3+) is observed as the VO concentration increases, while the Fe oxidation state remains fixed at Fe3+. Our findings provide a reliable way to quantify oxygen stoichiometry in complex oxides, offering a pathway to design materials with precisely tailored structure–property relationships.

Hossain, Mohammad Delower↗
NASA NTRS2008

L-Edge Xanes Measurements of the Oxidation State of Tungsten in Iron Bearing and Iron Free Silicate Glasses

Tungsten is important in constraining core formation of the Earth because this element is a moderately siderophile element (depleted ~ 10 relative to chondrites) and, as a member of the Hf-W isotopic system, it is useful in constraining the timing of core formation. A number of previous experimental studies have been carried out to determine the silicate solubility and metal-silicate partitioning behavior of W, including its concomitant oxidation state. However, results of previous studies are inconsistent on whether W occurs as W(4+) or W(6+). It is assumed that W(4+) is the cation valence relevant to core formation. Given the sensitivity to silicate composition of high valence cations, knowledge of the oxidation state of W over a wide range of fO2 is critical to understanding the oxidation state of the mantle and core formation processes. This study seeks to measure the W valence and change in valence state over the range of fO2 most relevant to core formation, around IW-2.

Danielson, L. R.↗
NASA NTRS1986

Do the higher oxidation states of the photosynthetic O2-evolving system contain bound H2O?

A modified mass spectrometer was used to determine whether the higher oxidation states of the photosynthetic O2-evolving system contain substrate water that is not freely exchangeable with the external medium. Our data indicated that the higher oxidation states contain no appreciable bound, non-exchangeable H2O. This suggests that H2O oxidation takes place via a rapid, concerted, all-or-none mechanism rather than by a mechanism involving stable, partially oxidized, H2O-derived intermediates. These findings set definite constraints on possible mechanisms of O2 evolution.

NASA Discipline Life Support Systems↗
NASA NTRS1993

Oxidation state of the Earth's upper mantle during the last 3800 million years: Implications for the origin of life

A popular, as well as scientifically rigorous, scenario for the origin of life on Earth involves the production of organic molecules by interaction of lightning (or other forms of energy) with a chemically reducing atmosphere in the early history of Earth. Experiments since the 1950's have convincingly demonstrated that the yield of organic molecules is high when the atmosphere contains molecular hydrogen, methane, ammonia, and water vapor. Additional work has also shown that such a highly reducing atmosphere might not, however, have been sufficiently long-lived in the presence of intense solar ultraviolet radiation for life to have formed from it. One way of maintaining such an atmosphere would be to have a continual replenishment of the reduced gases by prolonged volcanic outgassing from a reducing of Earth's interior. The length of time that this replenishment might need to continue is in part constrained by the flux of asteroids onto the Earth's surface containing sufficient energy to destroy most, if not all, life that had developed up to that point in time. If a reducing atmosphere is a key ingredient for the origin of life on Earth, the time of the last environmental sterilization due to large impacts would be an important constraint. In a deep marine setting (e.g., hydrothermal vent), the last global sterilization might have occurred at 4200-4000 Ma. On the Earth's surface, the last global sterilization event might have occurred at 4000-3700 Ma. If these are meaningful constraints, how likely is it that a reducing atmosphere could have survived on the Earth until about 3800 Ma ago? Due to the importance of replenishing this atmosphere with reducing components by volcanic outgassing from the mantle, geochemical information on the history of the mantle's oxidation state would be useful for addressing this question. Geochemical and experimental data discussed in this abstract suggest that extrusive mafic volcanics derived from the upper mantle have had oxidation states near the fayalite-magnetite quartz buffer throughout the last 3800 Ma. At magmatic temperatures, the gases released from volcanoes having this oxidation state would have been, as they are today, composed dominantly of carbon dioxide and water vapor, and would not contain the ingredients for maintaining a reducing atmosphere. Consequently, geochemical data do not favor the survival of a reducing atmosphere until about 3800 Ma. Alternative venues and pathways for the origin of life need to be investigated (e.g., hydrothermal vents along oceanic ridges).

Delano, J. W.↗
NASA NTRS2005

Micro-XANES Measurements on Experimental Spinels and the Oxidation State of Vanadium in Coexisting Spinel and Silicate Melt

Spinel can be a significant host phase for V which has multiple oxidation states V(sup 2+), V(sup 3+), V(sup 4+) or V(sup 5+) at oxygen fugacities relevant to natural systems. The magnitude of D(V) spinel/melt is known to be a function of composition, temperature and fO2, but the uncertainty of the oxidation state under the range of natural conditions has made elusive a thorough understanding of D(V) spinel/melt. For example, V(sup 3+) is likely to be stable in spinels, based on exchange with Al in experiments in the CaO-MgO-Al2O3-SiO2 system. On the other hand, it has been argued that V(sup 4+) will be stable across the range of natural oxygen fugacities in nature. In order to build on our previous work in more oxidized systems, we have carried out experiments at relatively reducing conditions from the FMQ buffer to 2 log fO2 units below the IW buffer. These spinel-melt pairs, where V is present in the spinel at natural levels (approx. 300 ppm V), were analyzed using an electron microprobe at NASA-JSC and micro- XANES at the Advanced Photon Source at Argonne National Laboratory. The new results will be used together with previous results to understand the valence of V in spinel-melt systems across 12 orders of magnitude of oxygen fugacity, and with application to natural systems.

Righter, K.↗
NASA NTRS2006

Magnetite in Martian Meteorite Mil 03346 and Gusev Adirondack Class Basalt: Moessbauer Evidence for Variability in the Oxidation State of Adirondack Lavas

The Moessbauer spectrometers on the Mars Exploration Rovers Spirit (Gusev crater) and Opportunity (Meridiani Planum) have returned information on the oxidation state of iron, the mineralogical composition of Fe-bearing phases, and the distribution of Fe among oxidation states and phases [1,2,3]. To date, ~100 and ~85 surface targets have been analyzed by the Spirit and Opportunity spectrometers, respectively. Twelve component subspectra (8 doublets and 4 sextets) have been identified and most have been assigned to mineralogical compositions [4]. Two sextet subspectra result from the opaque and strongly magnetic mineral magnetite (Fe3O4 for the stoichiometric composition), one each for the crystallographic sites occupied by tetrahedrally-coordinated Fe3+ and by octahedrally-coordinated Fe3+ and Fe2+. At Gusev crater, the percentage of total Fe associated with magnetite for rocks ranges from 0 to ~ 35% (Fig. 1) [3]. The range for soils (~5 to ~12% of total Fe from Mt, with one exception) is narrower. The ubiquitous presence of Mt in soil firmly establishes the phase as the strongly magnetic component in martian soil

Morris, R. V.↗
NASA NTRS2006

Magnetite in Martian Meteorite Mil 03346 and Gusev Adirondack Class Basalt: Mossbauer Evidence for Variability in the Oxidation State of Adirondack Lavas

The Moessbauer spectrometers on the Mars Exploration Rovers Spirit (Gusev crater) and Opportunity (Meridiani Planum) have returned information on the oxidation state of iron, the mineralogical composition of Fe-bearing phases, and the distribution of Fe among oxidation states and phases [1,2,3]. To date, approx.100 and approx.85 surface targets have been analyzed by the Spirit and Opportunity spectrometers, respectively. Twelve component subspectra (8 doublets and 4 sextets) have been identified and most have been assigned to mineralogical compositions [4]. Two sextet subspectra result from the opaque and strongly magnetic mineral magnetite (Fe3O4 for the stoichiometric composition), one each for the crystallographic sites occupied by tetrahedrally-coordinated Fe3+ and by octahedrally-coordinated Fe3+ and Fe2+. At Gusev crater, the percentage of total Fe associated with magnetite for rocks ranges from 0 to approx. 35% (Fig. 1) [3]. The range for soils (approx.5 to approx.12% of total Fe from Mt, with one exception) is narrower. The ubiquitous presence of Mt in soil firmly establishes the phase as the strongly magnetic component in martian soil [4,5].

Morris, R. V.↗
NASA NTRS2004

Micro-XANES Measurements on Experimental Spinels and the Oxidation State of Vanadium in Spinel-Melt Pairs

Spinel can be a significant host phase for V as well as other transition metals such as Ni and Co. However, vanadium has multiple oxidation states V(2+), V(3+), V(4+) or V(5+) at oxygen fugacities relevant to natural systems. We do know that D(V) spinel/melt is correlated with V and TiO2 content and fO2, but the uncertainty of the oxidation state under the range of natural conditions has made elusive a thorough understanding of D(V) spinel/melt. For example, V(3+) is likely to be stable in spinels, based on exchange with Al in experiments in the CaO-MgO-Al2O3-SiO2 system. On the other hand, it has been argued that V(4+) will be stable across the range of natural oxygen fugacities in nature. In order to gain a better understanding of D(V) spinel/melt we have equilibrated spinel-melt pairs at controlled oxygen fugacities, between HM to NNO, where V is present in the spinel at natural levels (approx. 300 ppm V). These spinel-melt pairs were analyzed using micro-XANES at the Advanced Photon Source at Argonne National Laboratory. The new results will be used together with spinel compositional data (Ti, V content) and oxygen fugacity, to unravel the effects of these variables on D(V) spinel/melt.

Righter, K.↗
DOE OSTI2024

Formal Oxidation States and Coordination Environments in the Catalytic Reduction of CO to Methanol

Fundamental insight into multi-electron, multi-proton redox reactions with organometallic catalysts is greatly facilitated by knowledge of the formal oxidation state of the metal center in each of the elementary reaction steps that comprise the catalytic cycle. X-ray absorption near edge structure (XANES) is utilized herein to quantify the oxidation states and coordination environment of the organometallic resting state and intermediates in a newly proposed catalytic reduction of carbon monoxide to methanol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2014

Chromium Oxidation State in Planetary Basalts: Oxygen Fugacity Indicator and Critical Variable for Cr-Spinel Stability

Cr is a ubiquitous and relatively abundant minor element in basaltic, planetary magmas. At the reduced oxidation states (<FMQ) of many planetary basalts Cr is present in melts as both divalent and trivalent forms. The ratio of trivalent to divalent Cr present in the melt has many consequences for the stability and Cr concentration of magmatic phases such as spinel, clinopyroxene, and olivine. However, understanding the Cr valence in quenched melts has historically been plagued with analytical issues, and only recently has reliable methodology for quantifying Cr valence in quenched melts been developed. Despite this substantial difficulty, the pioneering works of Hanson and Jones and Berry and O'Neill provided important insights into the oxidation state of Cr in in silicate melts. Here we present a series of 1-bar gas mixing experiments performed with a Fe-rich basaltic melt in which have determined the Cr redox ratio of the melt at over a range of fO2 values by measuring this quantity in olivine with X-ray Absorption Near Edge Spectroscopy (XANES). The measured Cr redox ratio of the olivine phenocrysts can be readily converted to the ratio present in the conjugate melt via the ratio of crystal-liquid partition coefficients for Cr3+ and Cr2+. We have applied these results to modeling Cr spinel stability and Cr redox ratios in a primitive, iron-rich martian basalt.

Bell, A. S.↗
NASA NTRS1984

Effects of high CO2 levels on surface temperature and atmospheric oxidation state of the early earth

One-dimensional radiative and photochemical models are used to determine how much CO2 must have been present to maintain a temperate early climate and to examine the consequences that are implied for the controls on atmospheric oxidation state. It is shown that CO2 concentrations of the order of 1000 PAL are required to keep the average surface temperature close to the present value, if albedo changes and heating by reduced greenhouse gases were relatively unimportant. The oxidation state of such a high-CO2, prebiotic atmosphere should have been largely determined by the balance between the H2O2 rainout rate and the rate at which hydrogen escaped to space, with only a weak dependence on the volcanic outgassing rate or on other speculative sources of H2. The implied upper limit on the ground-level O2 mixing ratio is approximately 10 to the -11th and is subject to less uncertainty than the results of previous models.

Kasting, J. F.↗