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Microanalysis of Fe-3+/Total(Fe) in extraterrestrial samples is important due to sample size constraints of sample return missions. We compare Fe XANES spectra with Co optical spectra that predict valence electron levels based on 'Z1' model. Additional information is contained in the original extended abstract.
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.
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.
Zag and Monahans meteorites (H5) contains xenolithic dark clasts and halite (NaCl) crystals [e.g., 1]. The proposed source of the H chondrites is asteroid 6 Hebe [2]. The modern orbits of 1 Ceres and 6 Hebe essentially cross, with aphelion/perihelion of Ceres and Hebe of 2.99/2.55 and 2.91/1.94 AU (Astronomical Units), respectively. Therefore, Ceres might be the source of the clasts and halite in Zag and Monahans meteorites. Recent results from NASA's Dawn mission shows that bright spots in Ceres's crater may be hydrated magnesium sulfate with some water ice, and an average global surface contains ammoniated phyllosilicates that is likely of outer Solar System origin. One dark clast and all halite crystals in Zag and Monahans meteorites contain carbon-rich particles. We report organic analyses of these carbon-rich particles using carbon, nitrogen, and oxygen X-ray absorption near edge structure (C-, N-, and O-XANES), in order to constrain the origin of the clast and halite crystals.
Some impact-melt glasses in shergottites are rich in Martian atmospheric noble gases and sulfur suggesting a possible association with regolith-derived secondary mineral assemblages in the shocked samples. Previously, we studied two glasses, # 506 (Lith C in Lith A) and # 507 (Lith C in Lith B) from EET79001 [1,2] and suggested that sulfur initially existed as sulfate in the glass precursor materials and, on shock-melting of the precursors, the sulfate was reduced to sulfides in the shock glasses. To examine the validity of this hypothesis, we used V K microXANES techniques to measure the valence states of vanadium in the Lith C glasses from Lith A and Lith B in EET79001 [3] to complement and com-pare with previous analogous measurements on,78 glass (Lith C in Lith A) [4,5]. We reported the preliminary results in [3]. Vanadium is ideal for addressing the redox issue because it has multiple valence states and is a well-studied element. Vanadium in basalts exists mostly as V(sup 3+), V(sup 4+) and V(sup 5+) in terrestrial samples, mainly as V(sup 3+) with minor V(sup 2+) and minor V(sup 4+) in lunar samples and as roughly equal mixtures of V(sup 3+) and V(sup 4+) in Martian meteorites. In this report, we discuss the application of the V K XANES results to decipher the nature of shock reduction occurring in the silicate glasses during the impact process.
Titan, the largest moon of Saturn, is a fascinating object. It is the only other object in the Solar System, besides Earth, with a dense (1.5 bar at the surface) atmosphere whose composition is dominated by N2, with CH4 as the second most abundant gas. A complex organic chemistry between N2 and CH4, induced by solar UV photons and energetic particles, results in the formation of a large variety of organic compounds, including hydrocarbons (e.g., C2H2, C2H4, C2H6, C3H4, C6H6), nitriles (e.g., HCN, HNC, HC3N, CH3CN, C2N2), as well as larger molecules that include aromatic and heteroaromatic compounds [1]. This complex organic chemistry also leads to the formation of aerosols that play an important role in Titan’s atmospheric dynamics, climate, as well as surface composition and processes. Because of its N2-based dense atmosphere, and its CH4 cycle that resembles the hydrological cycle on Earth, Titan is often considered to be an analog of early Earth. In recent years, Titan’s atmosphere and surface were monitored in detail by the NASA Cassini mission, which orbited the Saturnian system from 2004 to 2017, as well as the ESA Huygens probe, which plunged into Titan’s atmosphere and landed on its surface in 2005.
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.
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.
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.
X-ray pleochroism is a predictable source of scatter in synchrotron microXANES analyses of elemental oxidation states. The magnitude of the effect is illustrated and a procedure to compensate for it has been implemented, reducing errors significantly. Additional information is contained in the original extended abstract.
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+).
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.
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.
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.
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.
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.
Analyses with a scanning transmission x-ray microscope (STXM) using x-ray absorption near edge structure (XANES) spectroscopy were applied for the molecular characterization of two kinds of carbonaceous particles of unknown origin, termed category 3, which were collected from the Hayabusa spacecraft sample catcher. Carbon-XANES spectra of the category 3 particles displayed typical spectral patterns of heterogeneous organic macromolecules; peaks corresponding to aromatic/olefinic carbon, heterocyclic nitrogen and/or nitrile, and carboxyl carbon were all detected. Nitrogen-XANES spectra of the particles showed the presence of N-functional groups such as imine, nitrile, aromatic nitrogen, amide, pyrrole, and amine. An oxygen-XANES spectrum of one of the particles showed a ketone group. Differences in carbon- and nitrogen-XANES spectra of the category 3 particles before and after transmission electron microscopic (TEM) observations were observed, which demonstrates that the carbonaceous materials are electron beam sensitive. Calcium-XANES spectroscopy and elemental contrast mapping identified a calcium carbonate grain from one of the category 3 particles. No fluorine-containing molecular species were detected in fluorine-XANES spectra of the particles. The organic macromolecular features of the category 3 particles were distinct from commercial and/or biological ‘fresh (non-degraded)’ polymers, but the category 3 molecular features could possibly reflect degradation of contaminant polymer materials or polymer materials used on the Hayabusa spacecraft. However, an extraterrestrial origin for these materials cannot currently be ruled out.
X-ray absorption near edge structure (XANES) spectroscopy is a powerful technique for characterizing the chemical state and symmetry of individual elements within materials, but requires collecting data at many energy points which can be time-consuming. While adaptive sampling methods exist for efficiently collecting spectroscopic data, they often lack domain-specific knowledge about the structure of XANES spectra. Here we demonstrate a knowledge-injected Bayesian optimization approach for adaptive XANES data collection that incorporates understanding of spectral features like absorption edges and pre-edge peaks. We show this method accurately reconstructs the absorption edge of XANES spectra using only 15–20% of the measurement points typically needed for conventional sampling, while maintaining the ability to determine the x-ray energy of the sharp peak after the absorption edge with errors less than 0.03 eV, the absorption edge with errors less than 0.1 eV; and overall root-mean-square errors less than 0.005 compared to traditionally sampled spectra. Our experiments on battery materials and catalysts demonstrate the method’s effectiveness for both static and dynamic XANES measurements, improving data collection efficiency and enabling better time resolution for tracking chemical changes. This approach advances the degree of automation in XANES experiments, reducing the common errors of under- or over-sampling points near the absorption edge and enabling dynamic experiments that require high temporal resolution or limited measurement time.