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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Carbon Mineralization of Sulfate Wastes Containing Pb: Synchrotron Pb M3-Edge XANES Analysis of Simultaneous Heavy Metal and Carbon Sequestration

Sulfate wastes are produced in large quantities and contain toxic heavy metals such as lead (Pb), posing environmental risks. Because of favorable solubility differences, these wastes can be repurposed for engineered carbon dioxide (CO 2 ) sequestration. Understanding the fate and mobility of heavy metals during this process is important. This study focuses on Pb and the effect of zinc (Zn) on Pb in carbon mineralization. Synthesized gypsum was treated with a carbonate-rich solution at pH 11.5 to convert the sulfates to carbonates. Aqueous solutions and mineral solids were analyzed. Synchrotron-based micro-X-ray fluorescence and a novel application of Pb M3-edge X-ray absorption near-edge structure provided detailed insights into Pb distribution and mineral forms. Results showed significant reductions in aqueous Pb and Zn concentrations, indicating effective metal sequestration. Carbon mineralization transformed Pb from soluble anglesite (PbSO 4 ) into insoluble cerussite (PbCO 3 ) and hydrocerussite (Pb 3 (CO 3 ) 2 (OH) 2 ). Pb primarily precipitated onto calcium carbonate surfaces through surface-mediated precipitation reactions. While the presence of Zn modified crystallization dynamics, it did not impede Pb sequestration and potentially enhanced surface reactivity, facilitating greater Pb immobilization. These findings highlight carbon mineralization as a sustainable approach to immobilize toxic metals in sulfate wastes while advancing CO 2 sequestration efforts.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Toward a Machine Learning Approach to Interpreting X-ray Spectra of Trace Impurities by Converting XANES to EXAFS

The fact that the photoabsorption spectrum of a material contains information about the atomic structure, commonly understood in terms of multiple scattering theory, is the basis of the popular extended X-ray absorption spectroscopy (EXAFS) technique. How much of the same structural information is present in other complementary spectroscopic signals is not obvious. Here we use a machine learning approach to demonstrate that within theoretical models that accurately predict the EXAFS signal, the extended near-edge region does indeed contain the EXAFS-accessible structural information. We do this by exhibiting deep operator neural networks (DeepONets) that have learned the relationship between the extended and near edge portions of the X-ray absorption spectrum to predict the former from the latter. We find that we can accurately predict the EXAFS spectrum between 6 and 14 Å –1 from the first 6 Å –1 (≈100 eV) of the absorption spectrum of Cu 2 + substitutional defects in the Fe 3+ mineral hematite (α-Fe 2 O 3 ). This surprising finding implies that theoretical analyses of X-ray absorption spectra could be implemented that extract the same conclusions as high-quality EXAFS studies from spectra collected over a much smaller range of photon energies. This relaxes a host of experimental limitations related to the X-ray source and measurement sample, including collection time, minimum dopant concentration, source brilliance, and energy range. We describe the theoretical data sets and DeepONet construction and show that the resulting DeepONets produce EXAFS that recovers linear combination fits to experimental data with accuracy approaching the original ab initio calculations. We discuss the implications of our findings for minor constituent characterization and for understanding the information content of spectroscopic data more broadly, including how this approach might be applied to measured experimental spectra. In conclusion, to encourage similar efforts, the simulated X-ray spectra, machine learning, and fitting code are publicly available.

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

Intermediate Yb valence in the Zintl phases Yb 14 MSb 11 (M=Zn,Mn,Mg): XANES, magnetism, and heat capacity

Yb 14 Mn Sb 11 is a magnetic Zintl compound as well as being one of the best high temperature p -type thermoelectric materials. According to the Zintl formalism, which defines intermetallic phases where cations and anions are valence satisfied, this structure type is nominally made up of 14 Yb 2 + , 1 MnSb 4 9 - , 1 Sb 3 7 - , and 4 Sb 3 - atoms. When Mn is replaced by Mg or Zn, the Zintl defined motifs become 13 Yb 2 + , 1 Yb 3 + , 1 (Mg, Zn) Sb 4 10 - , 1 Sb 3 7 - , and 4 Sb 3 - . The predicted existence of Yb 3 + based on simple electron counting rules of the Zintl formalism calls the Yb valence of these compounds into question. X-ray absorption near-edge structure, magnetic susceptibility, and specific heat measurements on single crystals of the three analogs show signatures of intermediate valence Yb behavior and in particular, reveal the heavy fermion nature of Yb 14 MgSb 11 . In these isostructural compounds, Yb can exhibit a variety of electronic configurations from intermediate ( M = Zn ), mostly 2+ ( M = Mn ), to 3+ ( M = Mg ). In all cases, there is a small amount of intermediate valency at the lowest temperatures. The amount of intermediate valency is constant for M = Mn , Mg and temperature dependent for M = Zn . The evolution of the Yb valence correlated to the transport properties of these phases is highlighted. The presence of Yb in this structure type allows for fine tuning of the carrier concentration and thereby the possibility of optimized thermoelectric properties along with unique magnetic phenomena.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Probing rutile solid-phase crystallization of atomically mixed Mn-alloyed TiO 2 coatings through XANES analysis

Phase transformation via dopant introduction is an emerging strategy for tuning the electronic and catalytic properties of oxides. However, developing a general theory of ternary alloys and their microstructure evolution remains challenging due to the knowledge gaps in how point defects such as dopants lead to the formation of complex or metastable phases. We investigate the influence of Mn concentration and annealing temperature on the microstructure evolution of amorphous Mn-alloyed TiO 2 synthesized via Atomic Layer Deposition. In conclusion, our findings reveal a new crystallization pathway resulting in a direct amorphous TiO 2 to rutile transformation without an intermediate anatase phase and our multi-parameter thermal processing conditions show potential for AI-assisted data acquisition and analysis for studying complex oxide coatings.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Catalytic Reaction Intermediates Revealed with Femtosecond M-edge XANES (Final Technical Report)

The major goals of this work were to measure the electronic structure of earth-abundant catalysts at key steps in their catalytic cycles using ultrafast UV/Visible, Extreme Ultraviolet, and X-ray spectroscopy. Our central idea was that by using these sophisticated probes, we could uncover hidden reaction mechanisms and provide guidance for catalyst design. A second major goal was the development of Extreme Ultraviolet (XUV) spectroscopy as an accessible, tabletop probe of transition metal electronic structure. Spectra in this 30-100 eV energy range probe 3d→3p transitions in 3d metals and 5p/4f→5d transitions in 5d metals, and share the oxidation state, spin state, and ligand field specificity of hard X-ray spectroscopy. The Vura-Weis group previously established the basic utility of this technique for measuring the excited-state cascades of transition metal chromophores, and in this grant we intended to extend its scope to catalytic intermediates.

36 MATERIALS SCIENCE↗
NASA NTRS2007

The Oxidation State of Tungsten in Iron Bearing and Iron Free Silicate Glasses: Results from W L-Edge Xanes Measurements

Tungsten is important in constraining core formation of the Earth because this element is a moderately siderophile element (depleted approx. 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 (figure 1) are inconsistent on whether W occurs as W(4+) or W(6+).

Danielson, Lisa R.↗
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 NTRS2008

Comparison of Carbon XANES Spectra from an Iron Sulfide from Comet Wild 2 with an Iron Sulfide Interplanetary Dust Particle

Among one of the first particles removed from the aerogel collector from the Stardust sample return mission was an approx. 5 micron sized iron sulfide. The majority of the spectra from 5 different sections of this particle suggests the presence of aliphatic compounds. Due to the heat of capture in the aerogel we initially assumed these aliphatic compounds were not cometary but after comparing these results to a heated iron sulfide interplanetary dust particle (IDP) we believe our initial interpretation of these spectra was not correct. It has been suggested that ice coating on iron sulfides leads to aqueous alteration in IDP clusters which can then lead to the formation of complex organic compounds from unprocessed organics in the IDPs similar to unprocessed organics found in comets [1]. Iron sulfides have been demonstrated to not only transform halogenated aliphatic hydrocarbons but also enhance the bonding of rubber to steel [2,3]. Bromfield and Coville (1997) demonstrated using Xray photoelectron spectroscopy that "the surface enhancement of segregated sulfur to the surface of sulfided precipitated iron catalysts facilitates the formation of a low-dimensional structure of extraordinary properties" [4]. It may be that the iron sulfide acts in some way to protect aliphatic compounds from alteration due to heat.

Wirick, S.↗
NASA NTRS2009

Carbon XANES Data from Six Aerogel Picokeystones Cut from the Top and Bottom Sides of the Stardust Comet Sample Tray

Great care and a large effort was made to minimize the amount of organic matter contained within the flight aerogel used to collect Comet 81P/Wild 2 samples. Even so, by the very nature of the production process and silica aerogel s affinity for volatile organics keeping silica aerogel free from organics is a monumental task. Silica aerogel from three production batches was flown on the Stardust sample return mission. All 3 types had layered densities varying from 5mg/ml to 50 mg/ml where the densest aerogel was farthest away from the collection area. A 2 step gelation process was used to make the flight aerogel and organics used in this process were tetraethylorthosilicate, ethanol and acetonitrile. Both ammonium hydroxide and nitric acid were also used in the aerogel production process. The flight aerogel was baked at JPL at 300 C for 72 hours, most of the baking was done at atmosphere but twice a day the oven was pumped to 10 torr for hour [1]. After the aerogel was baked it was stored in a nitrogen purged cabinet until flight time. One aerogel cell was located in the SRC away from any sample collection area as a witness to possible contamination from out gassing of the space craft, re-entry gases and any other organic encounter. This aerogel was aerogel used in the interstellar collection sample tray and is the least dense of the 3 batches of aerogel flown. Organics found in the witness tile include organics containing Si-CH3 bonds, amines and PAHS. Besides organic contamination, hot spots of calcium were reported in the flight aerogel. Carbonates have been detected in comet 81P/Wild2 samples . During preflight analyses, no technique was used to analyze for carbonates in aerogel. To determine if the carbonates found in 81P/Wild2 samples were from the comet, it is necessary to analyze the flight aerogel for carbonate as well as for organics.

Wirick, S.↗
NASA NTRS2015

V Xanes in Spinels as an Oxy-Barometer in Meteorites with Implications for Redox Variations in the Inner Solar System

The variation of oxygen fugacity within inner solar system materials spans a range of nearly 15 orders of magnitude. Igneous and metamorphic rocks commonly contain a mineral assemblage that allows oxygen fugacity to be calculated or con-strained such as FeTi oxides, olivine-opx-spinel, or some other oxy-barometer. Some rocks, however, contain a limited mineral assemblage and do not provide constraints on fO2 using mineral equilibria. Good examples of the latter are orthopyroxenites or dunites, such as diogenites, ALH 84001, chassignites, or brachinites. In fact it is no surprise that the fO2 of many of these achondrites is not well known, other than being "reduced" and below the metal saturation value. In order to bridge this gap in our understanding, we have initiated a study of V in chromites in achondrite. Because the V pre-edge peak intensity and energy in chromites varies with fO2, and this has been calibrated over a large fO2 range, we can apply this relation to rocks for which we otherwise have no fO2 constraints.

Righter, K.↗
NASA NTRS2017

Developing V-Xanes Oxybarometry for Probing Materials Formed in Reducing Environments in the Early Solar Disk

Vanadium exhibits four oxidation states (V(sup 2+), V(sup 3+), V(sup 4+) and V(sup 5+)) that have been shown to preferentially partition between melt phases dependent on redox conditions, spanning oxygen fugacity across more than 10 log units. We are developing synchrotron-based x-ray absorption spectroscopy of low-fugacity standards for the determination of V oxidation state in highly reducing conditions relevant to the early solar nebula.

Butterworth, A. L.↗