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At least 55 records · Page 3

The Oxidation State of Sulfur in Apollo Samples 71035 and 71055

Lunar apatites contain 100s-1000s ppm sulfur [1-3]. This was initially puzzling because lunar basalts are thought to form, including at the time of apatite crystallization, in low oxygen fugacity (fO2) conditions where sulfur exists in its reduced form (S2-), a substitution not previously observed in natural apatite. It has been recently shown, using S-XANES measurements of the oxidation state of sulfur in apatites and proximal mesostasis in the lunar basalts 12039 and 10044, that sulfur is indeed present as S2- in both the mesostasis glass and apatite when measurements were performed far from cracks or pits in the thin section [4]. This observation is consistent with other mineralogical indications of the low fO2 during formation of these samples (~IW-1) such as the presence of Fe-metal, ulvöspinel, ilmenite, fayalite, and silica in the thin sections. In the same study, in addition to clear spectral evidence for the dominance of S2-, analyses of apatite grains in both samples that occurred near cracks or pits in the thin section sometimes revealed non-negligible spectral evidence (e.g., S6+/ΣS > 0.03; [4]) for the presence of S6+. Because S6+ was not observed in the mesostasis glass near the apatite grains measured, or in any phase far from cracks or pits in the studied thin sections, this S6+ was interpreted as either primary S2- in the sulfide altered to S6+ in the thin section, or S6+ of secondary origin, deposited in the fractures of the samples [4, 5]. Whether this is of lunar or terrestrial origin is unknown but has implications for lunar petrogenesis if lunar [e.g., 5], or sample handling and curation if terrestrial. To test between lunar and terrestrial origins for observed S6+ in Apollo-era thin sections, we will measure the oxidation state of sulfur in apatite and associated phases in a specially frozen sample from a boulder sampled at Station 1A during the Apollo 17 mission as part of the NASA Apollo Next Generation Sample Analysis (ANGSA) program. Here, we present “control” measurements of samples 71035 and 71055, using Apollo era thin sections of aliquots of these rocks that were processed upon return to Earth and since stored under N2 atmospheres at room temperature. These will be compared to measurements using newly made thin sections of aliquots of the same rocks (71035 and 71055). In addition, 71036, which has been in cold storage (-20℃) since the return of the Apollo 17 mission to Earth, has been recently made available through the ANGSA program. With 71036 we can test the effect of storage temperature on potential oxidation of S2- to S6+ in the relatively oxidizing and warm conditions of Earth’s surface.

apollo↗

Constraints on the Detection of the Solar Nebula's Oxidation State Through Asteroid Observations

Introduction: Asteroids represent the only in situ surviving population of planetesimals from the formation of the inner solar system and therefore include materials from the very earliest stages of solar system formation. Hence, these bodies can provide constraints on the processes and conditions that were present during this epoch and can be used to test current models and theories describing the late solar nebula, the early solar system and subsequent planetary accretion. From detailed knowledge of asteroid mineralogic compositions the probable starting materials, thermal histories, and oxidation states of asteroid parent bodies can be inferred. If such data can be obtained from specific mainbelt source regions, then this information can be used to map out the formation conditions of the late solar nebula within the inner solar system and possibly distinguish any trends in oxidation state that may be present.

Abell, P. A.↗

Evolution of the Oxidation State of the Earth's Mantle: Challenges of High Pressure Quenching

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. Experiments of more mafic compositions and at higher pressures commonly form a polyphase quench intergrowth composed primarily of pyroxenes, with interstitial glass which hosts nearly all of the more volatile minor elements. In our previous experiments on shergottite compositions, variable fO2, T, and P is less than 4 GPa, Fe3+/TotFe decreased slightly with increasing P, similar to terrestrial basalt. For oxidizing experiments less than 7GPa, Fe3+/TotFe 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. Experiments with Knippa basalt as the starting composition were conducted at 1-8 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 from 7-8 GPa quenched to polycrystalline phases, with the major phase pyroxene containing approximately equal Fe3+/2+. A number of different approaches have been employed to produce glassy samples that can be measured by EELS and XANES. A more intermediate andesite was used in one experiment, and decompression during quenching was attempted after, but both resulted in a finer grained polyphase texture. Experiments are currently underway to test different capsule materials may affect quench texture. A preliminary experiment using liquid nitrogen to greatly enhance the rate of cooling of the assembly has also been attempted and this technique will be refined in further experiments.

Danielson, L. R.↗

Oxidation state of iron in plagioclase from lunar basalts.

Determination of the oxidation state of iron in the plagioclase from the coarse-grained basalts 10044 and 12021, using Mossbauer spectroscopy. The location of iron in the crystal structure was also investigated. The spectra show that iron is in the high-spin ferrous state, and they located at least two distinct positions with different coordination numbers. Some excess resonant absorption is probably due to Fe(3+), although the Fe(3+) doublet could not be positively resolved.

Hafner, S. S.↗

Layer Resolved Cr Oxidation State Modulation in Epitaxial SrFe 0.67 Cr 0.33 O 3−δ Thin Films

Understanding how doping influences physicochemical properties of ABO 3 perovskite oxides is critical for tailoring their functionalities. In this study, SrFe 0.67 Cr 0.33 O 3−δ epitaxial thin films were used to examine the effects of Fe and Cr competition on structure and B-site cation oxidation states. The films exhibit a perovskite-like structure near the film/substrate interface, while a brownmillerite-like structure with horizontal oxygen vacancy channels predominates near the surface. Electron energy loss spectroscopy shows Fe remains Fe 3+ , while Cr varies from ∼Cr 3+ (tetrahedral layers) to ∼Cr 4+ (octahedral layers) within brownmillerite phases and becomes ∼Cr 4.5+ in perovskite-like phases. Theoretical simulations indicate that Cr–O bond arrangements and the way oxygen vacancies interact with Cr and Fe drive Cr charge disproportionation. High-valent Cr cations introduce additional densities of states near the Fermi level, reducing the optical bandgap from ∼2.0 eV (SrFeO 2.5 ) to ∼1.7 eV (SrFe 0.67 Cr 0.33 O 3−δ ). In conclusion, these findings offer insights into B-site cation doping in the perovskite oxide framework.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Site-Selective Doping and Oxidation State Control of Copper in Gold Nanorods

We report the synthesis of plasmonic gold–copper nanostructures with tunable copper spatial distribution and oxidation state. Au–Cu alloy shells were deposited in aqueous solution onto colloidal gold nanorods that functioned as seeds, and the resulting shell morphology was found to depend strongly on the nanorod aspect ratio. For relatively fat gold nanorods (16 x 31 nm), Au–Cu growth was preferentially localized near the rod midsections, forming belt-like structures, whereas for skinnier nanorods (9 x 32 nm), Au–Cu growth produced patchy surface coverage around the entire rod. The shell thickness was tuned from 1 to 4 nm; upon air exposure, thicker shells exhibited a higher Cu(I) fraction compared to the initial shell. Incorporation of the Au–Cu shell led to pronounced shifts in the plasmonic features of the gold nanorods. These tunable plasmonic Au–Cu nanorods provide a materials basis for Cu-based plasmonic materials in the context of electrochemical CO₂ reduction.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Organic carbon oxidation state shapes fermentative methanogenic microbiomes and controls greenhouse gas fluxes

Organic compounds with a negative nominal oxidation state of carbon (NOSC) are thermodynamically recalcitrant in anaerobic ecosystems, but few studies have measured the influence of NOSC on carbon degradation rates, gaseous product yields, or microbiome composition. We amended anaerobic rice paddy sediment microcosms with water-soluble monomeric organic carbon compounds varying in NOSC. Consistent with thermodynamic and stoichiometric predictions, negative NOSC compounds are catabolized more slowly but produce more methane per mole of carbon. Negative NOSC microbiomes have higher alpha diversity, more syntrophs and methanogens, and fewer fermentative bacteria. Strikingly, fermentative bacterial taxa display genomically encoded NOSC catabolic preferences both in the lab and field. Negative NOSC-preferring fermenters have longer predicted doubling times, consistent with the thermodynamic recalcitrance of their preferred substrates. We propose that microbial NOSC catabolic preferences may reflect the thermodynamic niche of microorganisms and we anticipate that extending research on microbial catabolic preferences to a greater variety of organic carbon substrates and diverse microbiomes will improve our understanding of microbial carbon cycling and trait evolution.

Hu, Ruiwen↗

The x ray microprobe determination of chromium oxidation state in olivine from lunar basalt and kimberlitic diamonds

The synchrotron x-ray microprobe is being used to obtain oxidation state information on planetary materials with high spatial resolution. Initial results on chromium in olivine from various sources including laboratory experiments, lunar basalt, and kimberlitic diamonds are reported. The lunar olivine was dominated by Cr(2+) whereas the diamond inclusions had Cr(2+/Cr(3+) ratios up to about 0.3. The simpliest interpretation is that the terrestrial olivine crystallized in a more oxidizing environment than the lunar olivine.

Sutton, S. R.↗

Bolide impacts and the oxidation state of carbon in the earth's early atmosphere

A one-dimensional photochemical model was used to examine the effect of bolide impacts on the oxidation state of earth's primitive atmosphere. The impact rate should have been high prior to 3.8 Ga before present, based on evidence derived from the moon. Impacts of comets or carbonaceous asteroids should have enhanced the atmospheric CO/CO2 ratio by bringing in CO ice and/or organic carbon that can be oxidized to CO in the impact plume. Ordinary chondritic impactors would contain elemental iron that could have reacted with ambient CO2 to give CO. Nitric oxide (NO) should also have been produced by reaction between ambient CO2 and N2 in the hot impact plumes. High NO concentrations increase the atmospheric CO/CO2 ratio by increasing the rainout rate of oxidized gases. According to the model, atmospheric CO/CO2 ratios of unity or greater are possible during the first several hundred million years of earth's history, provided that dissolved CO was not rapidly oxidized to bicarbonate in the ocean.

Kasting, James F.↗

Bolide impacts and the oxidation state of carbon in the Earth's early atmosphere

A one-dimensional photochemical model was used to examine the effect of bolide impacts on the oxidation state of Earth's primitive atmosphere. The impact rate should have been high prior to 3.8 Ga before present, based on evidence derived from the Moon. Impacts of comets or carbonaceous asteroids should have enhanced the atmospheric CO/CO2 ratio by bringing in CO ice and/or organic carbon that can be oxidized to CO in the impact plume. Ordinary chondritic impactors would contain elemental iron that could have reacted with ambient CO2 to give CO. Nitric oxide (NO) should also have been produced by reaction between ambient CO2 and N2 in the hot impact plumes. High NO concentrations increase the atmospheric CO/CO2 ratio by increasing the rainout rate of oxidized gases. According to the model, atmospheric CO/CO2 ratios of unity or greater are possible during the first several hundred million years of Earth's history, provided that dissolved CO was not rapidly oxidized to bicarbonate in the ocean. Specifically, high atmospheric CO/CO2 ratios are possible if either: (1) the climate was cool (like today's climate), so that hydration of dissolved CO to formate was slow, or (2) the formate formed from CO was efficiently converted into volatile, reduced carbon compounds, such as methane. A high atmospheric CO/CO2 ratio may have helped to facilitate prebiotic synthesis by enhancing the production rates of hydrogen cyanide and formaldehyde. Formaldehyde may have been produced even more efficiently by photochemical reduction of bicarbonate and formate in Fe(++)-rich surface waters.

Non-NASA Center↗

Clay-mediated reactions of HCN oligomers - The effect of the oxidation state of the clay

Montmorillonite clays which contain Fe(III) inhibit the oligomerization of aqueous solutions of HCN. The inhibitory effect is due to the rapid oxidation of diaminomaleonitrile, a key intermediate in HCN oligomerization, by the Fe(III) incorporated into the aluminosilicate lattice of the clay. The Fe(III) oxidizes diaminomaleonitrile to diiminosuccinonitrile, a compound which is rapidly hydrolyzed to HCN and oxalic acid derivatives. Diaminomaleonitrile is not oxidized when Fe(III) in the montmorillonite is reduced with hydrazine. The oxidation state of the clay is an important variable in experiments designed to simulate clay catalysis on the primitive earth.

Ferris, J. P.↗

Prediction of the Cu Oxidation State from EELS and XAS Spectra Using Supervised Machine Learning

Electron energy loss spectroscopy (EELS) and X-ray absorption spectroscopy (XAS) provide detailed information about distributions and locations of atoms, their coordination numbers and oxidation states, and the bonding characteristics [1]. However, analysis of XAS/EELS data often relies on matching the spectra of an unknown experimental sample to a series of simulated or experimental spectra of standard samples. Here, this limits analysis throughput and the ability to extract quantitative information from a sample.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Relationships Among Intrinsic Properties of Ordinary Chondrites: Oxidation State, Bulk Chemistry, Oxygen-isotopic Composition, Petrologic Type, and Chondrule Size

The properties of ordinary chondrites (OC) reflect both nebular and asteroidal processes. OC are modeled here as having acquired nebular water, probably contained within phyllosilicates, during agglomeration. This component had high Ai70 and acted like an oxidizing agent during thermal metamorphism. The nebular origin of this component is consistent with negative correlations in H, L, and LL chondrites between oxidation state (represented by olivine Fa) and bulk concentration ratios of elements involved in the metal-silicate fractionation (e.g., NdSi, Ir/Si, Ir/Mn, Ir/Cr, Ir/Mg, Ni/Mg, As/Mg, Ga/Mg). LL chondrites acquired the greatest abundance of phyllosilicates with high (delta)O-17 among OC (and thus became the most oxidized group and the one with the heaviest O isotopes); H chondrites acquired the lowest abundance, becoming the most reduced OC group with the lightest O isotopes. Chondrule precursors may have grown larger and more ferroan with time in each OC agglomeration zone. Nebular turbulence may have controlled the sizes of chondrule precursors. H-chondrite chondrules (which are the smallest among OC) formed from the smallest precursors. In each OC region, low-FeO chondrules formed before high-FeO chondrules during repeated episodes of chondrule formation. During thermal metamorphism, phyllosilicates were dehydrated; the liberated water oxidized metallic Fe-Ni. This caused correlated changes with petrologic type including decreases in the modal abundance of metal, increases in olivine Fa and low-Ca pyroxene Fs, increases in the olivine/pyroxene ratio, and increases in the kamacite Co and Ni contents. As water (with its heavy 0 isotopes) was lost during metamorphism, inverse correlations between bulk (delta)O-18 and bulk (delta)O-17 with petrologic type were produced. The H5 chondrites that were ejected from their parent body approx.7.5 Ma ago during a major impact event probably had been within a few kilometers of each other since they accreted approx.4.5 Ga ago. There are significant differences in the olivine compositional distributions among these rocks; these reflect stochastic nebular sampling of the oxidant (Le., phyllosilicates with high (delta)O-17) on a 0.1-1 km scale during agglomeration.

Rubin, Alan E.↗

Biologically Influenced Transport of the +3 Actinide Oxidation State from the WIPP Environment, Using Neodymium as an Analog

This report provides an update to a previously issued report on the bioassociation of the +3 actinide analog, neodymium, with Waste Isolation Pilot Plant (WIPP) microbial isolates (LCO ACP-32, Biologically Influenced Transport of the +3 Actinide Oxidation State from the WIPP Environment, Using Neodymium as an Analog ). Results contribute to updates for the biocolloid parameters for the 2026 Compliance Recertification Application (CRA-2026).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Oxidation state of the atmosphere and crust of Venus from Pioneer Venus results

Recent spacecraft observations of Venus permit a detailed model of sulfur chemistry in the atmosphere-lithosphere system. Pioneer Venus experiments confirm that, as predicted, COS and H2S are dominant over SO2 in the lower atmosphere, and that the equilibrium concentrations of S2 and S3 are significant. Many criteria serve to bracket the oxidation state of the crust: it is nearly certain that the S2(2-)/SO4(2-) buffer regulates the oxygen fugacity, and that FeO is at least as abundant as F2O3 in crustal silicates. A highly oxidized crust (as, for example, would result from O2 absorption complementary to escape of vast amounts of H2) is incompatible with the gas-phase sulfur chemistry. If the Pioneer Venus mass spectrometer estimates of the abundance of sulfur gases are correct, earth-like models for the bulk composition of Venus are seriously in error, and a far lower FeO content is required for Venus.

Lewis, J. S.↗

Effects of iron oxidation state on viscosity, lunar composition 15555

The viscous flow behavior of a 9.6-kg lunar rock containing 22.5 wt.% FeO was studied in the temperature ranges from 620 to 700 C and from 1215 to 1400 C. The material was synthesized under mildy reducing conditions to simulate the Fe(2+)/total Fe ratio of the lunar environment. The effect of iron oxidation state on flow behavior in the high viscosity region is studied for specimens of the 15555 composition with Fe(2+) concentration ratios of 0.94, 0.76, and 0.20. A change in ratio from 0.94 to 0.76 had no observable effect on viscosity, whereas a change from 0.76 to 0.20 was accompanied by a drastic increase in viscosity (some three orders of magnitude) at a given temperature, but without changing the form of the variation of viscosity with temperature. The flow behavior is analyzed as a function of the structural features of the glasses.

Cukierman, M.↗