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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 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Evolution and engineering of pathways for aromatic O -demethylation in Pseudomonas putida KT2440

In this study, biological conversion of lignin from biomass offers a promising strategy for sustainable production of fuels and chemicals. However, aromatic compounds derived from lignin commonly contain methoxy groups, and O-demethylation of these substrates is often a rate-limiting reaction that influences catabolic efficiency. Several enzyme families catalyze aromatic O-demethylation, but they are rarely compared in vivo to determine an optimal biocatalytic strategy. Here, two pathways for aromatic O-demethylation were compared in Pseudomonas putida KT2440. The native Rieske non-heme iron monooxygenase (VanAB) and, separately, a heterologous tetrahydrofolate-dependent demethylase (LigM) were constitutively expressed in P. putida, and the strains were optimized via adaptive laboratory evolution (ALE) with vanillate as a model substrate. All evolved strains displayed improved growth phenotypes, with the evolved strains harboring the native VanAB pathway exhibiting growth rates ~1.8x faster than those harboring the heterologous LigM pathway. Enzyme kinetics and transcriptomics studies investigated the contribution of selected mutations toward enhanced utilization of vanillate. The VanAB-overexpressing strains contained the most impactful mutations, including those in VanB, the reductase for vanillate O-demethylase, PP_3494, a global regulator of vanillate catabolism, and fghA, involved in formaldehyde detoxification. These three mutations were combined into a single strain, which exhibited approximately 5x faster vanillate consumption than the wild-type strain in the first 8 h of cultivation. Overall, this study illuminates the details of vanillate catabolism in the context of two distinct enzymatic mechanisms, yielding a platform strain for efficient O-demethylation of lignin-related aromatic compounds to value-added products.

09 BIOMASS FUELS↗
DOE OSTI2026

Alkali Metal Cation Effects on Dinitrogen Complexes and Organometallic Compounds

Alkali metal (AM) cations are often taken for granted as counterions in coordination chemistry and organometallic reactions. However, the AM cation can be more than a bystander in inorganic transformations. This Account focuses on research that has elucidated several types of AM cation effects and how these can be exploited to achieve novel structures and reactivity pathways. Here, a particular focus is on AM cation effects in low-coordinate iron β-diketiminate complexes, though we address general trends and potential applications in systems with other supporting ligands.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2004

Workshop on Oxygen in the Terrestrial Planets

This volume contains abstracts that have been accepted for presentation at the Workshop on Oxygen in the Terrestrial Planets, July 20-23,2004, Santa Fe, New Mexico. The contents include: 1) Experimental Constraints on Oxygen and Other Light Element Partitioning During Planetary Core Formation; 2) In Situ Determination of Fe(3+)/SigmaFe of Spinels by Electron Microprobe: An Evaluation of the Flank Method; 3) The Effect of Oxygen Fugacity on Large-Strain Deformation and Recrystallization of Olivine; 4) Plagioclase-Liquid Trace Element Oxygen Barometry and Oxygen Behaviour in Closed and Open System Magmatic Processes; 5) Core Formation in the Earth: Constraints from Ni and Co; 6) Oxygen Isotopic Compositions of the Terrestrial Planets; 7) The Effect of Oxygen Fugacity on Electrical Conduction of Olivine and Implications for Earth s Mantle; 8) Redox Chemical Diffusion in Silicate Melts: The Impact of the Semiconductor Condition; 9) Ultra-High Temperature Effects in Earth s Magma Ocean: Pt and W Partitioning; 10) Terrestrial Oxygen and Hydrogen Isotope Variations: Primordial Values, Systematics, Subsolidus Effects, Planetary Comparisons, and the Role of Water; 11) Redox State of the Moon s Interior; 12) How did the Terrestrial Planets Acquire Their Water?; 13) Molecular Oxygen Mixing Ratio and Its Seasonal Variability in the Martian Atmosphere; 14) Exchange Between the Atmosphere and the Regolith of Mars: Discussion of Oxygen and Sulfur Isotope Evidence; 15) Oxygen and Hydrogen Isotope Systematics of Atmospheric Water Vapor and Meteoric Waters: Evidence from North Texas; 16) Implications of Isotopic and Redox Heterogeneities in Silicate Reservoirs on Mars; 17) Oxygen Isotopic Variation of the Terrestrial Planets; 18) Redox Exchanges in Hydrous Magma; 19) Hydrothermal Systems on Terrestrial Planets: Lessons from Earth; 20) Oxygen in Martian Meteorites: A Review of Results from Mineral Equilibria Oxybarometers; 21) Non-Linear Fractionation of Oxygen Isotopes Implanted in Lunar Metal Grains: Solar, Lunar or Terrestrial Origin? 22) Isotopic Zoning in the Inner Solar System; 23) Redox Conditions on Small Bodies; 24) Determining the Oxygen Fugacity of Lunar Pyroclastic Glasses Using Vanadium Valence - An Update; 25) Mantle Redox Evolution and the Rise of Atmospheric O2; 26) Variation of Kd for Fe-Mg Exchange Between Olivine and Melt for Compositions Ranging from Alkaline Basalt to Rhyolite; 27) Determining the Partial Pressure of Oxygen (PO,) in Solutions on Mars; 28) The Influence of Oxygen Environment on Kinetic Properties of Silicate Rocks and Minerals; 29) Redox Evolution of Magmatic Systems; 30) The Constancy of Upper Mantlefo, Through Time Inferred from V/Sc Ratios in Basalts: Implications for the Rise in Atmospheric 0 2; 31) Nitrogen Solubility in Basaltic Melt. Effects of Oxygen Fugacity, Melt Composition and Gas Speciation; 32) Oxygen Isotope Anomalies in the Atmospheres of Earth and Mars; 33) The Effect of Oxygen Fugacity on Interdiffusion of Iron and Magnesium in Magnesiowiistite 34) The Calibration of the Pyroxene Eu-Oxybarometer for the Martian Meteorites; 35) The Europium Oxybarometer: Power and Pitfalls; 36) Oxygen Fugacity of the Martian Mantle from PigeoniteMelt Partitioning of Samarium, Europium and Gadolinium; 37) Oxidation-Reduction Processes on the Moon: Experimental Verification of Graphite Oxidation in the Apollo 17 Orange Glasses; 38) Oxygen and Core Formation in the Earth; 39) Geologic Record of the Atmospheric Sulfur Chemistry Before the Oxygenation of the Early Earth s Atmosphere; 40) Comparative Planetary Mineralogy: V/(CrCAl) Systematics in Chromite as an Indicator of Relative Oxygen Fugacity; 41) How Well do Sulfur Isotopes Constrain Oxygen Abundance in the Ancient Atmospheres? 42) Experimental Constraints on the Oxygen Isotope (O-18/ O-16) Fractionation in the Ice vapor and Adsorbant vapor Systems of CO2 at Conditions Relevant to the Surface of Mars; 43) Micro-XANES Measurements on Experimental Spinels andhe Oxidation State of Vanadium in Spinel-Melt Pairs; 44) Testing the Magma Ocean Hypothesis Using Metal-Silicate Partitioning of Te, Se and S; 45) Solubility of Oxygen in Liquid Iron at High Pressure and Consequences for the Early Differentiation of Earth and Mars Metallic Liquid Segregation in Planetesimals; 46) Oxygen Fugacity of Lunar Basalts and the Lunar Mantle. Range of fo2 and the Effectiveness of Oxybarometers; 47) Thermodynamic Study of Dissociation Processes of Molecular Oxygen in Vapor over Oxide Compounds; 48) Oxygen Profile of a Thermo-Haliophilic Community in the Badwater Salt Flat; 49) Oxygen Barometry Using Synchrotron MicroXANES of Vanadium; 50) Mass-Independent Isotopic Fractionation of Sulfur from Sulfides in the Huronian Supergroup, Canada; 51) Mass Independent Isotopes and Applications to Planetary Atmospheres; 52) Electrical Conductivity, Oxygen Fugacity, and Mantle Materials; 53) Crustal Evolution and Maturation on Earth: Oxygen Isotope Evidence; 54) The Oxygen Isotope Composition of the Moon: Implications for Planet Formation; 55) Oxygen Isotope Composition of Eucrites and Implications for the Formation of Crust on the HED Parent Body; and 56) The Role of Water in Determining the Oxygen Isotopic Composition of Planets.

Source record↗
NASA NTRS2023

Evolutionary Flexibility and Rigidity in the Bacterial Methylerythritol Phosphate (Mep) Pathway

Terpenoids are a diverse class of compounds with wide-ranging uses including as industrial solvents, pharmaceuticals, and fragrances. Efforts to produce terpenoids sustainably by engineering microbes for fermentation are ongoing, but industrial production still largely relies on nonrenewable sources. The methylerythritol phosphate (MEP) pathway generates terpenoid precursor molecules and includes the enzyme Dxs and two iron–sulfur cluster enzymes: IspG and IspH. IspG and IspH are rate limiting-enzymes of the MEP pathway but are challenging for metabolic engineering because they require iron–sulfur cluster biogenesis and an ongoing supply of reducing equivalents to function. Therefore, identifying novel alternatives to IspG and IspH has been an on-going effort to aid in metabolic engineering of terpenoid biosynthesis. We report here an analysis of the evolutionary diversity of terpenoid biosynthesis strategies as a resource for exploration of alternative terpenoid biosynthesis pathways. Using comparative genomics, we surveyed a database of 4,400 diverse bacterial species and found that some may have evolved alternatives to the first enzyme in the pathway, Dxs making it evolutionarily flexible. In contrast, we found that IspG and IspH are evolutionarily rigid because we could not identify any species that appear to have enzymatic routes that circumvent these enzymes. The ever-growing repository of sequenced bacterial genomes has great potential to provide metabolic engineers with alternative metabolic pathway solutions. With the current state of knowledge, we found that enzymes IspG and IspH are evolutionarily indispensable which informs both metabolic engineering efforts and our understanding of the evolution of terpenoid biosynthesis pathways.

Bailey Marshall↗
NASA NTRS2005

Variations in the Peak Position of the 6.2 micron Interstellar Emission Feature: A Tracer of N in the Interstellar Polycyclic Aromatic Hydrocarbon Population

This paper presents the results of an investigation of the molecular characteristics that underlie the observed peak position and profile of the nominal 6.2 micron interstellar emission band generally attributed to the CC stretching vibrations of polycyclic aromatic hydrocarbons (PAHs). It begins with a summary of recent experimental and theoretical studies ofthe spectroscopic properties of large (>30 carbon atoms) PAH cations as they relate to this aspect of the astrophysical problem. It then continues with an examination of the spectroscopic properties of a number of PAH variants within the context of the interstellar 6.2 micron emission, beginning with a class of compounds known as polycyclic aromatic nitrogen heterocycles (PANHs; PAHs with one or more nitrogen atoms substituted into their carbon skeleton). In this regard, we summarize the results of recent relevant experimental studies involving a limited set of small PANHs and their cations and then report the results of a comprehensive computational study that extends that work to larger PANH cations including many nitrogen-substituted variants of coronene(+) (C24H12(+)), ovalene(+) (C32H14(+)), circumcoronene(+) (C54H18(+)), and circum-circumcoronene(+) (C96H24(+)). Finally, we report the results of more focused computational studies of selected representatives from a number of other classes of PAH variants that share one or more of the key attributes of the PANH species studied. These alternative classes of PAH variants include (1) oxygen- and silicon-substituted PAH cations; (2) PAH-metal ion complexes (metallocenes) involving the cosmically abundant elements magnesium and iron; and (3) large, asymmetric PAH cations. Overall, the studies reported here demonstrate that increasing PAH size alone is insuEcient to account for the position of the shortest wavelength interstellar 6.2 micron emission bands, as had been suggested by earlier studies. On the other hand, this work reveals that substitution of one or more nitrogen atoms within the interior of the carbon skeleton of a PAH cation induces a significant blueshift in the position of the dominant CC stretching feature of these compounds that is suf6cient to account for the position of the interstellar bands. Subsequent studies of the effects of substitution by other heteroatoms (O and Si), metal ion complexation (Fe(+), Mg(+), and Mg(2+)), and molecular symmetry variation-all of which fail to reproduce the blueshift observed in the PANH cations-indicate that N appears to be unique in its ability to accommodate the position of the interstellar 6.2 micron bands while simultaneously satisfying the other constraints of the astrophysical problem. This result implies that the peak position of the interstellar feature near 6.2 micron traces the degree of nitrogen substitution in the population, that most of the PAHs responsible for the interstellar IR emission features incorporate nitrogen within their aromatic networks, and that a lower limit of 1%-2% of the cosmic nitrogen is sequestered within the interstellar PAH population. Finally, in view of the ubiquity and abundance of interstellar PAHs and the permanent dipoles and distinctive electronic structures of these nitrogen-substituted variants, this work impacts a wide range of observational phenomena outside of the infrared region of the spectrum including the forest of unidentified molecular rotational features and the anomalous Galactic foreground emission in the microwave, and the diffuse interstellar bands (DIBs) and other structure in the interstellar extinction curve in the ulhviolet/visible. These astrophysical ramifications are discussed, and the dipole moments and rotational constants are tabulated to facilitate further investigations of the astrophysical role of nitrogen-substituted aromatic compounds.

Hudgins, Douglas M.↗
DOE OSTI2025

Description of the Electronic Structure of Oxyhemoglobin Using Fe L-Edge X-ray Absorption Spectroscopy

The electronic structure of oxyhemoglobin has been controversial since the discovery of the compound’s diamagnetism in 1936. Here, this study uses partial fluorescence yield Fe L-edge X-ray absorption spectroscopy (XAS) in the 3s→2p fluorescence on oxyhemoglobin solutions, measured using a transition-edge sensor detector, to obtain a quantitative experimental description of the electronic structure of the O 2 -bound iron site. The spectrum is very different from typical low-spin Fe II and Fe III heme spectra, and multiplet simulations indicate a mixed ground configuration with ∼57% low-spin Fe III and ∼43% low-spin Fe II character. This is also very different from the Fe II character found for the picket-fence porphyrin model complex. The oxyhemoglobin L-edge XAS data further show that the O 2 ligand engages in a weak σ- but strong π-bond with the iron ion, leading to the overall strong Fe–O 2 bond required for O 2 transport.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2005

Field demonstration of DNAPL dehalogenation using emulsified zero-valent iron

This paper describes the results of the first field-scale demonstration conducted to evaluate the performance of nanoscale emulsified zero-valent iron (EZVI) injected into the saturated zone to enhance in situ dehalogenation of dense, nonaqueous phase liquids (DNAPLs) containing trichloroethene (TCE). EZVI is an innovative and emerging remediation technology. EZVI is a surfactant-stabilized, biodegradable emulsion that forms emulsion droplets consisting of an oil-liquid membrane surrounding zero-valent iron (ZVI) particles in water. EZVI was injected over a five day period into eight wells in a demonstration test area within a larger DNAPL source area at NASA's Launch Complex 34 (LC34) using a pressure pulse injection method. Soil and groundwater samples were collected before and after treatment and analyzed for volatile organic compounds (VOCs) to evaluate the changes in VOC mass, concentration and mass flux. Significant reductions in TCE soil concentrations (>80%) were observed at four of the six soil sampling locations within 90 days of EZVI injection. Somewhat lower reductions were observed at the other two soil sampling locations where visual observations suggest that most of the EZVI migrated up above the target treatment depth. Significant reductions in TCE groundwater concentrations (57 to 100%) were observed at all depths targeted with EZVI. Groundwater samples from the treatment area also showed significant increases in the concentrations of cis-1,2-dichloroethene (cDCE), vinyl chloride (VC) and ethene. The decrease in concentrations of TCE in soil and groundwater samples following treatment with EZVI is believed to be due to abiotic degradation associated with the ZVI as well as biodegradation enhanced by the presence of the oil and surfactant in the EZVI emulsion.

Water Pollutants/isolation & purification↗
NASA NTRS2008

Intermediate Temperature Fluids Life Tests - Theory

There are a number of different applications that could use heat pipes or loop heat pipes (LHPs) in the intermediate temperature range of 450 to 750 K, including space nuclear power system radiators, and high temperature electronics cooling. Potential working fluids include organic fluids, elements, and halides, with halides being the least understood, with only a few life tests conducted. Potential envelope materials for halide working fluids include pure aluminum, aluminum alloys, commercially pure (CP) titanium, titanium alloys, and corrosion resistant superalloys. Life tests were conducted with three halides (AlBr3, SbBr3, and TiCl4) and water in three different envelopes: two aluminum alloys (Al-5052, Al-6061) and Cp-2 titanium. The AlBr3 attacked the grain boundaries in the aluminum envelopes, and formed TiAl compounds in the titanium. The SbBr3 was incompatible with the only envelope material that it was tested with, Al-6061. TiCl4 and water were both compatible with CP2-titanium. A theoretical model was developed that uses electromotive force differences to predict the compatibility of halide working fluids with envelope materials. This theory predicts that iron, nickel, and molybdenum are good envelope materials, while aluminum and titanium halides are good working fluids. The model is in good agreement with results form previous life tests, as well as the current life tests.

Tarau, Calin↗
NASA NTRS2004

Field Demonstration of DNAPL Dehalogenation Using Emulsified Zero-Valent Iron

This paper describes the results of the first field-scale demonstration conducted to evaluate the performance of nano-scale emulsified zero-valent iron (EZVI) injected into the saturated zone to enhance in situ dehalogenation of dense, non-aqueous phase liquids (DNAPLs) containing trichloroethene (TCE). EZVI is an innovative and emerging remediation technology. EZVI is a surfactant-stabilized, biodegradable emulsion that forms emulsion droplets consisting of an oil-liquid membrane surrounding zero-valent iron (ZVI) particles in water. EZVI was injected over a five day period into eight wells in a demonstration test area within a larger DNAPL source area at NASA's Launch Complex 34 (LC34) using a pressure pulse injection method. Soil and groundwater samples were collected before and after treatment and analyzed for volatile organic compounds (V005) to evaluate the changes in VOC mass, concentration and mass flux. Significant reductions in TCE soil concentrations (>80%) were observed at four of the six soil sampling locations within 90 days of EZVI injection. Somewhat lower reductions were observed at the other two soil sampling locations where visual observations suggest that most of the EZVI migrated up above the target treatment depth. Significant reductions in TCE groundwater concentrations (57 to 100%) were observed at all depths targeted with EZVI. Groundwater samples from the treatment area also showed significant increases in the concentrations of cis-1,2-dichloroethene (cDCE), vinyl chloride (VC) and ethene. The decrease in concentrations of TCE in soil and groundwater samples following treatment with EZVI is believed to be due to abiotic degradation associated with the ZVI as well as biodegradation enhanced by the presence of the oil and surfactant in the EZVI emulsion.

Quinn, Jacqueline↗
NASA NTRS1980

Advanced screening of electrode couples

The chromium (Cr(3+)/Cr(2+)) redox couple (electrolyte and electrode) was investigated to determine its suitability as negative electrode for the iron (Fe(3+)/Fe(2+))-chromium (Cr(3+)/Cr(2+)) redox flow battery. Literature search and laboratory investigation established that the solubility and stability of aqueous acidic solutions of chromium(3) chloride and chromium(2) chloride are sufficient for redox battery application. Four categories of electrode materials were tested; namely, metals and metalloid materials (elements and compounds), alloys, plated materials, and Teflon-bonded materials. In all, the relative performance of 26 candidate electrode materials was evaluated on the basis of slow scan rate linear sweep voltammetry in stirred solution. No single material tested gave both acceptable anodic an acceptable cathodic performance. However, the identification of lead as a good cathodic electrocatalyst and gold as a good anodic electrocatalyst led to the invention of the lead/gold combination electrocatalyst. This type of catalyst can be fabricated in several ways and appears to offer the advantages of each metal without the disadvantages associated with their use as single materials. This lead/gold electrocatalyst was tested by NASA-Lewis Research Center in complete, flowing, redox batteries comprising a stack of several cells. A large improvement in the battery's coulombic and energy efficiency was observed.

Giner, J. D.↗
NASA NTRS1994

Biotransformation of an uncured composite material

The feasibility of biologically degrading prepreg wastes was studied. The work was conducted with the intention of obtaining baseline data that would facilitate the achievement of two long-range goals. These goals are: (1) the biological remediation of the hazardous components in the prepreg wastes, and (2) providing the potential for recycling the prepreg waste fibers. The experiments examined a prepreg that employs an bismaleimide resin system. Initial results demonstrated an obvious deterioration of the prepreg material when incubated with several bacterial strains. The most active cultures were identified as a mixture of 'Bacillus cereus' and 'Pseudomonas sp'. Gas chromatography analyses revealed seven primary compounds in the resin mixture. Biotransformation studies, using the complete prepreg material, demonstrated on obvious loss of all seven organic compounds. Gas chromatography-mass spectrometry analyses resulted in structure assignments for the two primary components of the resin. Both were analogs of Bisphenol A; one being bismaleimide, and the other being Bisphenol A containing a diglycidyl moiety. The 'diglycidyl analog' was purified using thin-layer chromatography and the biotransformation of this compound (at 27 ug/ml bacterial culture) was monitored. After a seven-day incubation, approximately 40% of the organic compound was biotransformed. These results demonstrate the biotransformation of the prepreg resin and indicate that biological remediation of the prepreg wastes is feasible.

Welsh, Clement J.↗
NASA NTRS1972

The moon as a high temperature condensate

The accretion during condensation mechanism is used to explain the differences in composition of the terrestrial planets and the moon. Many of the properties of the moon, including the enrichment in Ca, Al, Ti, U, Th, Ba, Sr and the REE and the depletion in Fe, Rb, K, Na and other volatiles can be understood if the moon represents a high temperature condensate from the solar nebula. Thermodynamic calculations show that Ca, Al and Ti rich compounds condense first in a cooling nebula. The high temperature mineralogy is gehlenite, spinel perovskite, Ca-Al-rich pyroxenes and anorthite. The model is consistent with extensive early melting, shallow melting at 3 A.E. and with presently high speed internal temperatures. It is predicted that the outer 250 km is rich in plagioclase and FeO. The low iron content of the interior in this model raises the interior temperatures estimated from electrical conductivity by some 800 C. The lunar crust is 80 percent gabbroic anorthosite, 20 percent basalt and is about 250-270 km thick. The lunar mantle is probably composed of spinel, merwinite and diopside with a density of 3.4 g/cu cm.

Anderson, D. L.↗
NASA NTRS1993

Extrapolation of space weathering processes to other small solar system bodies

A diverse range of processes were invoked as the dominant factor or as important contributory factors in the modification of the optical surface and regolith of the moon. These include impact vitrification by large and small projectiles, solar wind implantation and the reduction of oxidized iron during energetic events, sputtering and crystal lattice damage by energetic cosmic rays, shock metamorphism of minerals, mixing of diverse lithologies by impacts, and contamination by external materials. These processes are also potentially important on the rocky surfaces of other small solar system bodies. For icy bodies, several additional processes are also possible, including formation of complex organic compounds from methane and ammonia-bearing ices by ultraviolet irradiation and the condensation of vapor species to form frost layers in the polar or cooler regions of objects at appropriate heliocentric distances. The lunar case, even when completely understood, will not extend in a simple linear fashion to other small rocky objects, nor will the optical surfaces of those objects all be affected to the same degree by each process. The major factors that will control the relative efficacy of a possible mechanism include the efficiency of ejecta retention and the degree to which the regolith materials experience multiple events (primarily a function of body size, escape velocity, and impactor velocities); the mean duration of typical regolith particle exposure at the optical surface and within reach of the micrometeorite, cosmic ray, solar wind, or UV fluxes (a function of the rate and scale of regolith mixing, production, and removal processes); the incident flux of solar (low energy) cosmic rays, solar wind, or UV radiation (inverse square of heliocentric distance) or of galactic (high energy) cosmic rays (slowly increasing flux with heliocentric distance); and the compositional and mineralogical nature of the surface being affected. In general, those processes that depend upon either the retention of impact ejecta or on the presence of multigenerational regoliths should be substantially less effective on smaller bodies with lower escape velocities. However, there are important exceptions to this generalization. For example, a process that involves the hypervelocity impact of small particles into a fine-grained regolith may be able to effectively retain highly shocked or melted material due to the nature of shock wave propagation in such a heterogeneous material.

Gaffey, M. J.↗
NASA NTRS1978

X-ray photoelectron spectroscopy study of radiofrequency-sputtered refractory compound steel interfaces

Radiofrequency sputtering was used to deposit Mo2C, Mo2B5, and MoSi2 coatings on 440C steel substrates. Both sputter etched and preoxidized substrates were used, and the films were deposited with and without a substrate bias of -300 V. The composition of the coatings was measured as a function of depth by X-ray photoelectron spectroscopy combined with argon ion etching. In the interfacial region there was evidence that bias produced a graded interface in Mo2B5 but not in Mo2C. Oxides of iron and of all film constituents except carbon were presented in all cases but the iron oxide concentration was higher and the layer thicker on the preoxidized substrates. The film and iron oxides were mixed in the MoSi2 and Mo2C films but layered in the Mo2B5 film. The presence of mixed oxides correlates with enhanced film adhesion.

Wheeler, D. R.↗
NASA NTRS2020

Fungal Exposure to Meteorite Thin Sections: Developing an Experimental to Observe Biogeochemical Changes

The Astromaterials Acquisition & Curation Office maintains collections of meteorite samples collected as part of the Antarctic Search for Meteorites (ANSMET) program. The chief goal of the curation department is to maintain these meteorites in pristine condition. The Astromaterials Research and Exploration Science (ARES) Directorate has implemented a microbial monitoring program for the meteorite collections that has resulted in the isolation of >100 fungal isolates [1], however it is currently unknown if these isolates could present danger to the collections through bioweathering or secretion of organic compounds. We grew a strain of Fusarium oxysporium isolated from nitrogen gas filters feeding the Meteorite Lab nitrogen gas in the presence of a H5 meteorite thin section to determine if this fungus has the capability of altering the mineral structure of this common meteorite. This first trial was to determine and understand the effects of Fusarium oxysporum growth on the iron content within H5 chondrites and evaluate what additional components are needed in the development of future trial runs. This experiment determined new considerations for handling samples, the nature of microscopic scans before and after the incubation period, and the quality of the samples utilized for the experiment. The results of this experiment were promising and warrant further investigation with a more refined process and timeline.

Barbre, K. S. R.↗
NASA NTRS2003

Aluminum Alloy and Article Cast Therefrom

A cast article from an aluminum alloy, which has improved mechanical properties at elevated temperatures, has the following composition in weight percent: Silicon 14 - 25.0, Copper 5.5 - 8.0, Iron 0.05 - 1.2, Magnesium 0.5 - 1.5, Nickel 0.05 - 0.9, Manganese 0.05 - 1.0, Titanium 0.05 - 1.2, Zirconium 0.05 - 1.2, Vanadium 0.05 - 1.2, Zinc 0.05 - 0.9, Phosphorus 0.001 - 0.1, and the balance is Aluminum, wherein the silicon-to-magnesium ratio is 10 - 25, and the copper-to-magnesium ratio is 4 - 15. The aluminum alloy contains a simultaneous dispersion of three types of Al3X compound particles (X=Ti, V, Zr) having a LI2, crystal structure, and their lattice parameters are coherent to the aluminum matrix lattice. A process for producing this cast article is also disclosed, as well as a metal matrix composite, which includes the aluminum alloy serving as a matrix and containing up to about 60% by volume of a secondary filler material.

Lee, Jonathan A.↗
DOE OSTI2025

The role of Ca-bridged organic matter in an alkaline soil, as revealed by multimodal chemical imaging

Mineral–organic matter (OM) studies have predominantly focused on acidic soils that are abundant in iron (Fe) oxides and aluminum (Al) oxides. We have probed mineral–OM interactions in an alkaline or calcareous soil of the Aridisols class. Unlike the role of Fe and Al, the role of Ca-minerals (particularly calcite), which are ubiquitous in alkaline soils, in OM sequestration is not well understood. Multiple recent model studies with aqueous Ca2+ or synthetic calcite and a suite of OM compounds have shown Ca-OM assemblages to be spatially correlated with calcite at the microscale. To study the chemical state of both Ca and Fe and their competing role in soil organic matter (SOM) stabilization, we performed laboratory characterization using x-ray diffraction, Mössbauer spectroscopy, x-ray photoelectron spectroscopy, scanning electron microscopy, and scanning transmission electron microscopy, alongside synchrotron-based microscale chemical imaging using scanning transmission x-ray microscopy combined with near-edge x-ray absorption fine structure. Ca mineral–organic associations were found to be ubiquitous in this system and are likely critical for understanding SOM stabilization/degradation in alkaline soils. From our findings on mineralogy, speciation, and the nature of Ca-OM bridging, we identified differences in C and Ca chemistry based on the relative location of OM to Ca minerals. The OM near the calcite crystal was enriched in lipid and protein moieties, Ca-OM next to Fe minerals displayed a strong contribution from aromatic compounds, while on the surface of microbes, the carbonate was believed to be of microbial in origin, as also suggested by preliminary works reporting on the formation of amorphous calcite or nano-calcite. In Ca-OM admixed with carbonate, it was difficult to distinguish Ca-associated OM from amorphous calcite or nano-calcite.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1994

Magnetite: What it reveals about the origin of the banded iron formations

Magnetite, Fe3O4 is produced abiotically and biotically. Abiotically, magnetite is a late magmatic mineral and forms as a consequence of the cooling of iron rich magma. Biotically, magnetite is produced by several organisms, including magnetotactic bacteria. Hematite, Fe2O3, is also produced abiotically and biotically. Abiotically, hematite rarely occurs as a primary mineral in igneous rocks, but is common as an alteration product, fumarole deposit, and in some metamorphosed Fe-rich rocks. Biotically, hematite is produced by several types of microorganisms. Biologically-produced magnetite and hematite are formed under the control of the host organism, and consequently, have characteristics not found in abiotically produced magnetite and hematite crystals. To determine if the magnetite and hematite in the Banded Iron Formation was biologically or abiotically produced, the characteristics of biologically-produced magnetite and hematite (concentrated from Aquaspirillum magnetotacticum) and abiotically-produced magnetite and hematite obtained from Wards Scientific Supply Company, were compared with characteristics of magnetite and hematite concentrated from the Gunflint Banded Iron Formation (Ontario, Canada) using thermal and crystallographic analytical techniques. Whole rock analysis of the Gunflint Banded Iron Formation by x-ray diffraction (XRD) and differential thermal analysis (DTA) revealed the presence of quartz, hematite, siderite and dolomite as the major minerals, and magnetite, greenalite, pyrite, pyrrhotite and apatite as the minor minerals. Analysis of a crude magnetic fraction of the Gunflint showed the minerals quartz, hematite, siderite, dolomite, and magnetite. Analysis of the crude magnetic fraction from Aquaspirillum magnetotacticum revealed organic compounds plus hematite and magnetite. The mineral identification and particle size distribution data obtained from the DTA along with XRD data indicate that the magnetite and hematite from the Gunflint BIF share some similarities with biologically formed magnetite and hematite.

Schwartz, D. E.↗