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NASA NTRS2007

Considerations on Terrestrial Iron Depositing Analogs to Earliest Mars

Iron oxide and hydroxide minerals, including hematite, can mineralize and preservemicrofossils and physical biomarkers (Allen at al., 2004). Preserved remnants of phototrophic microorganisms are recognized as biosignatures of past life on Earth (Schopf, 2006). To date, two types of surface iron depositing environments have been studied as analogs to possible habitable environments on earliest Mars: the highly acidified Rio Tinto River (Iberian Belt, Spain) [Gomez Ortis et al., 2007], and the nearneutral iron depositing Chocolate Pots Hot Spring (Yellowstone National Park, US) [Parenteau at al., 2005]. While phototrophs in the Rio Tinto are only represented by eukaryotic algae (Amaral Zettler et all., 2002), Chocolate Pots is mainly populated with cyanobacteria (Pierson et all., 2000; Brown et all., 2007). Which of these environments is the closer analog to a potentially habitable early Mars? Paleobiological data, combined with recent "tree of life" interpretations, suggest that phototrophic eukaryotes evolved not earlier than 2.5 - 2.8 b.y. after Earth s accretion (4.6 b.y.), while cyanobacteria and /or their iron-tolerant predecessors evolved between 1 - 1.5 b.y. after accretion (Brown et al., 2007). Lindsay and Brasier (2002) postulated that microbial life on Mars surface could have lasted no more than 1-1.5 b.y. after Mars accretion (also 4.6 b.y.). Recent multispectral mapping of Mars suggests that near-neutral wet environments prevailed at approximately this time (Bibring, et al., 2006). Thus, near-neutral iron depositing hot springs such as Chocolate Pots Hot Spring seem to be the more likely habitable analogs for earliest Mars.

Brown, Igor I.↗

NASA NTRS2004

Signs of Life in Meridiani Planum: What Might Opportunity See (Or Miss)?

The Meridiani Planum hematite deposit has been designated as the prime landing site for Opportunity, one of the two Mars Exploration Rover (MER) spacecraft. Iron oxide and hydroxide minerals, including hematite, can mineralize and preserve microfossils and physical biomarkers. Previous research by ourselves and others, summarized below, has demonstrated such mineralization in a variety of terrestrial hematite deposits. Our most recent study has focused on the mineralization of microorganisms in rock varnish, the iron- and manganese-rich layers that coat rocks in many arid environments.

Allen, C. C.↗

NASA NTRS2021

Refining the Transit Timing and Photometric Analysis of TRAPPIST-1: Masses, Radii, Densities, Dynamics, and Ephemerides

We have collected transit times for the TRAPPIST-1 system with the Spitzer Space Telescope over four years. We add to these ground-based, HST, and K2 transit-time measurements, and revisit an N-body dynamical analysis of the seven-planet system using our complete set of times from which we refine the mass ratios of the planets to the star. We next carry out a photodynamical analysis of the Spitzer light curves to derive the density of the host starand the planet densities. We find that all seven planets’ densities may be described with a single rocky mass–radius relation which is depleted in iron relative to Earth, with Fe 21 wt% versus 32 wt% for Earth, and otherwise Earth-like in composition. Alternatively, the planets may have an Earth-like composition but enhanced in light elements,such as a surface water layer or a core-free structure with oxidized iron in the mantle. We measure planet masses toa precision of 3%–5%, equivalent to a radial-velocity(RV)precision of 2.5 cm s−1, or two orders of magnitude more precise than current RV capabilities. We find the eccentricities of the planets are very small, the orbits are extremely coplanar, and the system is stable on 10 Myr timescales. We find evidence of infrequent timing outliers, which we cannot explain with an eighth planet; we instead account for the outliers using a robust likelihood function. We forecast JWST timing observations and speculate on possible implications of the planet densities forthe formation, migration, and evolution of the planet system.

Eric Agol↗

NASA NTRS1973

Artificial meteor ablation studies

Artificial meteor ablation was performed on natural minerals, composed predominately of magnetite and hematite, using an arc heated plasma stream of air. Analysis of the ablated debris indicated most was composed of two or more minerals. The more volatile elements were depleted and the relative abundance of Fe increased as a result of both volatile depletion and a reduction in its oxidation state. Hematite was converted to magnetite in the ablation zone, and quartz and apatite minerals were converted to an Fe-rich glass consisting of varying amounts of Si, P, Cl, and Ca, depending upon the accessory minerals available at the time of melting. Artificially created ablation products from iron oxides exhibited unique properties depending on the composition of the original material and the environmental conditions of formation. In addition to the accepted elemental criteria, these properties were morphologic characteristics, textural parameters, and the existence of metastable minerals.

Blanchard, M. B.↗

NASA NTRS2000

Analysis of Siderite Thermal Decomposition by Differential Scanning Calorimetry

Characterization of carbonate devolitilization has important implications for atmospheric interactions and climatic effects related to large meteorite impacts in platform sediments. On a smaller scale, meteorites contain carbonates which have witnessed shock metamorphic events and may record pressure/temperature histories of impact(s). ALH84001 meteorite contains zoned Ca-Mg-Fe-carbonates which formed on Mars. Magnetite crystals are found in the rims and cores of these carbonates and some are associated with void spaces leading to the suggestion by Brearley et al. that the crystals were produced by thermal decomposition of the carbonate at high temperature, possibly by incipient shock melting or devolitilization. Golden et al. recently synthesized spherical Mg-Fe-Ca-carbonates from solution under mild hydrothermal conditions that have similar carbonate compositional zoning to those of ALH84001. They have shown experimental evidence that the carbonate-sulfide-magnetite assemblage in ALH84001 can result from a multistep inorganic process involving heating possibly due to shock events. Experimental shock studies on calcium carbonate prove its stability to approx. 60 GPa, well in excess of the approx. 45 GPa peak pressures indicated by other shock features in ALH84001. In addition, Raman spectroscopy of carbonate globules in ALH84001 indicates no presence of CaO and MgO. Such oxide phases should be found associated with the magnetites in voids if these magnetites are high temperature shock products, the voids resulting from devolitilization of CO2 from calcium or magnesium carbonate. However, if the starting material was siderite (FeCO3), thermal breakdown of the ALH84001 carbonate at 470 C would produce iron oxide + CO2. As no documentation of shock effects in siderite exists, we have begun shock experiments to determine whether or not magnetite is produced by the decomposition of siderite within the < 45GPa pressure window and by the resultant thermal pulse to approx. 600 C experienced by ALH84001. Here, we report thermal and compositional characterization of unshocked siderite and its transition to magnetite. Additional information is contained in the original extended abstract.

Bell, M. S.↗

NASA NTRS2003

Synthesis of Sol-Gel Precursors for Ceramics from Lunar and Martian Soil Simulars

Recent NASA mission plans for the human exploration of our Solar System has set new priorities for research and development of technologies necessary to enable a long-term human presence on the Moon and Mars. The recovery and processing of metals and oxides from mineral sources on other planets is under study to enable use of ceramics, glasses and metals by explorer outposts. We report initial results on the production of sol-gel precursors for ceramic products using mineral resources available in martian or lunar soil. The presence of SiO2, TiO2, and Al2O3 in both martian (44 wt.% SiO2, 1 wt.% TiO2,7 wt.% Al2O3) and lunar (48 wt.% SiO2, 1.5 wt.% TiO2, 16 wt.% Al2O3) soils and the recent developments in chemical processes to solubilize silicates using organic reagents and relatively little energy indicate that such an endeavor is possible. In order to eliminate the risks involved in the use of hydrofluoric acid to dissolve silicates, two distinct chemical routes are investigated to obtain soluble silicon oxide precursors from lunar and martian soil simulars. Clear solutions of sol-gel precursors have been obtained by dissolution of silica from lunar soil simular in basic ethylene glycol (C2H4(OH)2) solutions to form silicon glycolates. Similarly, sol-gel solutions produced from martian soil simulars reveal higher contents of iron oxides. The elemental composition and structure of the precursor molecules were characterized. Further concentration and hydrolysis of the products was performed to obtain gel materials for evaluation as ceramic precursors.

Sibille, L.↗

NASA NTRS2004

Synthesis of Sol-Gel Precursors for Ceramics from Lunar and Martian Soil Simulars

Recent NASA mission plans for the human exploration of our Solar System has set new priorities for research and development of technologies necessary to enable a long-term human presence on the Moon and Mars. The recovery and processing of metals and oxides from mineral sources on other planets is under study to enable use of ceramics, glasses and metals by explorer outposts. We report initial results on the production of sol-gel precursors for ceramic products using mineral resources available in martian or lunar soil. The presence of SO2, TiO2, and Al2O3 in both martian (44 wt.% SiO2, 1 wt.% TiO2, 7 wt.% Al2O3) and lunar (48 wt.% SiO2, 1.5 wt.% TiO2, 16 wt.% Al2O3) soils and the recent developments in chemical processes to solubilize silicates using organic reagents and relatively little energy indicate that such an endeavor is possible. In order to eliminate the risks involved in the use of hydrofluoric acid to dissolve silicates, two distinct chemical routes are investigated to obtain soluble silicon oxide precursors from lunar and martian soil simulars. Clear solutions of sol-gel precursors have been obtained by dissolution of silica from lunar soil similar JSC-1 in basic ethylene glycol (C2H4(OH)2) solutions to form silicon glycolates. Similarly, sol-gel solutions produced from martian soil simulars reveal higher contents of iron oxides. Characterization of the precursor molecules and efforts to further concentrate and hydrolyze the products to obtain gel materials will be presented for evaluation as ceramic precursors.

Sibille, L.↗

NASA NTRS2005

Negative Searches for Evidence of Aqueous Alteration on Asteroid Surfaces

Small bodies in the Solar System preserve evidence of the processes occurring during early Solar System formation, unlike the larger planets that undergo continuous churning of their surfaces. We study these bodies to understand what processes affected different stages of Solar System formation. The action of aqueous alteration (the alteration of material by the interaction of that material with liquid formed by the melting of incorporated ice) of near-subsurface material has been inferred to occur on many asteroids based on the spectrophotometric evidence of phyllosilicates and iron alteration minerals. The definitive indication of aqueous alteration is the 3.0- micron absorption feature attributed to structural hydroxyl (OH) and interlayer and adsorbed water (H2O) in phyllosilicates (clays) (hereafter water of hydration). A weak absorption feature centered near 0.7 microns attributed to an Fe (2+) right arrow Fe (3+) charge transfer transition in oxidized iron in phyllosilicates has been observed in the reflectance spectra and photometry of approximately 50% of the main-belt C-class asteroids. An approximately 85% correlation between this 0.7- micron feature and the 3.0- micron water of hydration absorption feature was found among the low-albedo asteroids. The feature is usually centered near 0.68 microns in asteroid spectra, and ranges in wavelength from approximately 0.57 to 0.83 microns. Serendipitously, three of the Eight Color Asteroid Survey filters the v (0.550 microns), w (0.701 microns), and x (0.853 microns)-bracket this feature well, and can be used to determine the presence of this feature in the reflectance properties of an asteroid, and probe the aqueous alteration history of larger samples of asteroid data. Two efforts to search for evidence of aqueous alteration based on the presence of this 0.7- micron absorption feature are presented here.

Vilas, F.↗

NASA NTRS2017

Oxygen Extraction from Minerals

Oxygen, whether used as part of rocket bipropellant or for astronaut life support, is a key consumable for space exploration and commercialization. In Situ Resource Utilization (ISRU) has been proposed many times as a method for making space exploration more cost effective and sustainable. On planetary and asteroid surfaces the presence of minerals in the regolith that contain oxygen is very common, making them a potential oxygen resource. The majority of research and development for oxygen extraction from minerals has been for lunar regolith although this work would generally be applicable to regolith at other locations in space. This presentation will briefly survey the major methods investigated for oxygen extraction from regolith with a focus on the current status of those methods and possible future development pathways. The major oxygen production methods are (1) extraction from lunar ilmenite (FeTiO3) with either hydrogen or carbon monoxide, (2) carbothermal reduction of iron oxides and silicates with methane, and (3) molten regolith electrolysis (MRE) of silicates. Methods (1) and (2) have also been investigated in a two-step process using CO reduction and carbon deposition followed by carbothermal reduction. All three processes have byproducts that could also be used as resources. Hydrogen or carbon monoxide reduction produce iron metal in small amounts that could potentially be used as construction material. Carbothermal reduction also makes iron metal along with silicon metal and a glass with possible applications. MRE produces iron, silicon, aluminum, titanium, and glass, with higher silicon yields than carbothermal reduction. On Mars and possibly on some moons and asteroids, water is present in the form of mineral hydrates, hydroxyl (-OH) groups on minerals, andor water adsorbed on mineral surfaces. Heating of the minerals can liberate the water which can be electrolyzed to provide a source of oxygen as well. The chemistry of these processes, some key development and demonstration projects, the challenges remaining to be overcome, and possible future directions will be discussed with a goal of increased understanding of these important ISRU technologies and their potential applications to space exploration and settlement.

propellant production↗

NASA NTRS1979

Laboratory simulations of the pyrolytic release experiments - An interim report

During its operation on Mars the pyrolytic release experiment (PR) detected the fixation of small amounts of CO2 and/or CO. Laboratory simulations of the experimental conditions were made in an attempt to substantiate the previous conclusion that these reactions were chemical rather than biological. After pretreatment and incubation under various conditions, pyrolytic analysis was used to indicate the extent of surface catalyzed conversion of (C-14)O2 or (C-14)O to (C-14)-organic compounds. This abiotic synthesis was detected in experiments with three iron oxides, viz. hematite, magnetite and maghemite. When the incubation atmosphere was supplemented with water vapor, the levels of synthesis were in a range comparable to that detected in the Viking PR tests. An abiotic synthesis was also detected in experiments with a mixture of clays and minerals (Mars analog soil) or with montmorillonite artificially enriched in iron. With either substratum the reaction appeared to be the result of a photocatalytic synthesis of (C-14)-organics from (C-14)O and surface hydroxyl groups. This process was not dependent on the presence of water vapor in the incubation atmosphere. Although a duplication of the Viking data has not been achieved, these findings support the abiotic interpretation of the PR results.

Hubbard, J. S.↗

NASA NTRSDate not supplied

A Study of the Kinetics of the CO Oxidation Catalyst in a Human Spaceflight Fire Cartridges as a Method to Understand and Predict Performance

Fire Cartridges (FC) are an integral part of fire response on ISS, Orion and Gateway. When a pair of FCs are integrated with an Emergency Mask, they can be used to provide safe breathing air on these vehicles in a post-fire environment. The FCs have two primary mechanisms for removing contaminants from the air, an activated carbon (AC) bed which adsorbs the majority of fire byproducts, and a catalyst bed consisting of gold nanoparticles supported on iron oxide which oxidized CO to CO2 under near ambient conditions. While the FC catalyst has proven its ability to convert CO under relevant conditions, this paper attempts to address the apparent inconsistent performance of the catalyst seen in testing. Numerous variables effect the performance of the catalyst, including but not limited to: reaction environment, reactant gas composition, inert gas composition, catalyst age, and catalyst lot. This paper discusses the importance of these variables and attempts a fundamental mechanistic explanation for the effects of each variable. The fundamental mechanisms are then used to establish the magnitude of expected performance variability, which were validated against real test data of flight quality FCs.

Fire Cartridge↗

NASA NTRSDate not supplied

A Study of the Kinetics of the CO Oxidation Catalyst in a Human Spaceflight Fire Cartridges as a Method to Understand and Predict Performance

Fire Cartridge↗

NASA NTRS1976

Ion composition in a noctilucent cloud

Ion composition at mesospheric altitudes was measured and compared between high and mid-latitude sites under summer daytime conditions. Rocket-borne measurements were made with pumped quadrupole ion mass spectrometers. The mid-latitude data were obtained at Wallops Island, Virginia on June 30, 1973, at 1510 LMT. Large quantities of hydronium cluster ions were observed through 109+, with maximum concentrations at 55+ and 73+. Also, cluster ions of nitric oxide were observed through 84+. The high latitude launch occurred at Kiruna, Sweden on August 2, 1973, at 0700 LMT following visual sighting of a noctilucent cloud on the prior evening. The data near mesopause shows cluster ions, but also a preponderance of heavy ions between 90 and 145 AMU, with groupings 18 AMU apart but unrelated to the more typical cluster ions. One possible set of consistent identifications leads to iron and iron oxide hydrates. These results may suggest the presence of metallic particulates and ions which form hydrated clusters ions.

Goldberg, R. A.↗

NASA NTRS1993

Learning class descriptions from a data base of spectral reflectance of soil samples

Consideration is given to a program developed to learn class descriptions from positive and negative training examples of spectral reflectance data of bare soils. It is a combination of 'learning by example' and the generate-and-test paradigm and is designed to provide a robust learning environment that can handle error-prone data. The program was tested by having it learn class descriptions of various categories of organic carbon content, iron oxide content, and particle size distribution in soils. These class descriptions were then used to classify an array of targets. The program found the sequence of relationships between bands that contained the most important information to distinguish the classes. Physical explanations for the class descriptions obtained are presented.

Kimes, D. S.↗

NASA NTRS2026

Hematite Is a Mineralogical Marker of Ancient Climate Change on Mars

The ancient climate of Mars changed from warm to cold surface conditions. This climate transition is demonstrated by geomorphological evidence, but lacks suitable mineralogical indicators. We investigate the crystallographic properties of hematite (iron oxide) in Gale crater, measured by the Curiosity rover, and compare them to laboratory experiments. Hematite crystallite sizes are ~5 to ~65 nm in the oldest sedimentary rocks investigated by the rover (the Murray formation) and <10 nm in the younger overlying strata (Mirador and Carolyn Shoemaker formations). We attribute the larger crystallites in the Murray formation to post-depositional coarsening by groundwater in warm and wet conditions, which persisted for several million years. Hematite with small crystallites co-occurs with goethite (iron oxyhydroxide) in the overlying layers, consistent with colder and water- limited conditions.

Marek Szczerba↗

NASA NTRS1985

Basalts of Mars: Constraints on Volatile Evolution

The mineralogy of relatively unweathered rocks on Mars place important constraints on models of planetary oxidation state, volcanism and associated outgassing, accretion and associated volatile inventory, and geochemical changes over time. Reflectance spectra (300 to 2500 nm) provide direct mineralogic information about the surface materials. Spectra measured using Earth-based telescopes were analyzed by a multiple high-order derivative spectroscopy technique. Nine areas, measured during the 1978 opposition, were analyzed by the technique. Each contained suites of well-defined absorption bands. These bands can be interpreted in terms of constituent mineralogy by the technique of Adams. Among the features extracted from the spectra were bands attributed to iron oxides. Other bands can be attributed to silicates within chemically unweathered rocks/fines. Absorption features suggest the presence of Mg-olivine and plagioclase feldspar.

Huguenin, R. L.↗

NASA NTRS2023

Modeling Dust Mineralogical Composition: Sensitivity to Soil Mineralogy Atlases and Their Expected Climate Impacts

Soil dust aerosols are a key component of the climate system, as they interact with short- and long-wave radiation, alter cloud formation processes, affect atmospheric chemistry and play a role in biogeochemical cycles by providing nutrient inputs such as iron and phosphorus. The influence of dust on these processes depends on its physicochemical properties, which, far from being homogeneous, are shaped by its regionally varying mineral composition. The relative amount of minerals in dust depends on the source region and shows a large geographical variability. However, many state-of-the-art Earth system models (ESMs), upon which climate analyses and projections rely, still consider dust mineralogy to be invariant. The explicit representation of minerals in ESMs is more hindered by our limited knowledge of the global soil composition along with the resulting size-resolved airborne mineralogy than by computational constraints. In this work we introduce an explicit mineralogy representation within the state-of-the-art Multiscale Online Nonhydrostatic AtmospheRe CHemistry (MONARCH) model. We review and compare two existing soil mineralogy datasets, which remain a source of uncertainty for dust mineralogy modeling and provide an evaluation of multiannual simulations against available mineralogy observations. Soil mineralogy datasets are based on measurements performed after wet sieving, which breaks the aggregates found in the parent soil. Our model predicts the emitted particle size distribution (PSD) in terms of its constituent minerals based on brittle fragmentation theory (BFT), which reconstructs the emitted mineral aggregates destroyed by wet sieving. Our simulations broadly reproduce the most abundant mineral fractions independently of the soil composition data used. Feldspars and calcite are highly sensitive to the soil mineralogy map, mainly due to the different assumptions made in each soil dataset to extrapolate a handful of soil measurements to arid and semi-arid regions worldwide. For the least abundant or more difficult-to-determine minerals, such as iron oxides, uncertainties in soil mineralogy yield differences in annual mean aerosol mass fractions of up to ∼ 100 %. Although BFT restores coarse aggregates including phyllosilicates that usually break during soil analysis, we still identify an overestimation of coarse quartz mass fractions (above 2 µm in diameter). In a dedicated experiment, we estimate the fraction of dust with undetermined composition as given by a soil map, which makes up ∼ 10 % of the emitted dust mass at the global scale and can be regionally larger. Changes in the underlying soil mineralogy impact our estimates of climate-relevant variables, particularly affecting the regional variability of the single-scattering albedo at solar wavelengths or the total iron deposited over oceans. All in all, this assessment represents a baseline for future model experiments including new mineralogical maps constrained by high-quality spaceborne hyperspectral measurements, such as those arising from the NASA Earth Surface Mineral Dust Source Investigation (EMIT) mission.

Soil dust↗

NASA NTRS2000

Laser pyrolysis fabrication of ferromagnetic gamma'-Fe4N and FeC nanoparticles

Using the laser pyrolysis method, single phase gamma'-Fe4N nanoparticles were prepared by a two step method involving preparation of nanoscale iron oxide and a subsequent gas-solid nitridation reaction. Single phase Fe3C and Fe7C3 could be prepared by laser pyrolysis from Fe(CO)5 and 3C2H4 directly. Characterization techniques such as XRD, TEM and vibrating sample magnetometer were used to measure phase structure, particle size and magnetic properties of these nanoscale nitride and carbide particles. c2000 American Journal of Physics.

NASA Discipline Life Sciences Technologies↗