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Reduction of iron-bearing lunar minerals for the production of oxygen

The kinetics and mechanism of the reduction of simulants of the iron-bearing lunar minerals olivine ((Fe,Mg)2SiO4), pyroxene ((Fe,Mg,Ca)SiO3), and ilmenite (FeTiO3) are investigated, extending previous work with ilmenite. Fayalite is reduced by H2 at 1070 K to 1480 K. A layer of mixed silica glass and iron forms around an unreacted core. Reaction kinetics are influenced by permeation of hydrogen through this layer and a reaction step involving dissociated hydrogen. Reaction mechanisms are independent of Mg content. Augite, hypersthene, and hedenbergite are reduced in H2 at the same temperatures. The products are iron metal and lower iron silicates mixed throughout the mineral. Activation energy rises with calcium content. Ilmenite and fayalite are reduced with carbon deposited on partially reduced minerals via the CO disproportionation reaction. Reduction with carbon is rapid, showing the carbothermal reduction of lunar minerals is possible.

Massieon, Charles↗

Development of Machine Learning Algorithms to Segment and Study Images of Astromaterial Samples

Introduction: Micrometer-scale chemical analyses of chondritic meteorites and mission-returned asteroid samples can reveal details of the physical and chemical processes operating in the early solar system, including processes that gave rise to planets, moons, and minor bodies. These primitive astromaterials are comprised of chondrules, calcium- and aluminum-rich inclusions (CAI), and many other silicates, oxides, metals, sulfides, and fine-grained materials. The chemical and mineralogical complexity of these samples, vast populations of different components, and heterogeneity across mm to km scales, all limit our understanding of the origin and evolution of these materials. Here, we describe recent efforts to use machine learning techniques to automate the segmentation of chemical maps of chondritic meteorites, designed to aid studies of asteroid samples returned by spacecraft. By automating the task of segmentation it will become possible to rapidly analyze and interpret the sizes, shapes, mineralogy, chemistry, and other properties of every chondrule, calcium- and aluminum-rich inclusion (CAI) and other clast within and between asteroid samples. Sample return missions significantly accelerate and heighten the need to develop such new data analysis techniques, and associated data repositories. Techniques: Neural networks require abundant training data, i.e. images which have been segmented by a human user. We have manually segmented data available from previous petrologic and chemical work at NASA Johnson Space Center and the American Museum of Natural History [1-4]. These data were derived from energy- and wavelength-dispersive X-ray spectroscopy (EDS, WDS) mapping of samples from many chondrite groups. The Deeplabv3+ [5] neural network architecture was trained on human-labeled masks and used to create machine-labeled masks. Several different algorithms were investigated, with inputs ranging from common RGB image formats through to hyperspectral datasets, with raw data comprising greyscale maps of Mg, Ca, and Al, with or without Si, Fe, Ti for both EDS and WDS data, and extending to other elements in EDS only. Each greyscale image was paired with a binary mask for each labelled particle type. Results: The trained algorithms can segment (Fig 1), classify, and measure the dimensions of thousands of particles in chemical maps of a standard 1-inch round petrographic section in seconds to minutes, rather than many hours needed by a human. Accuracy of the algorithms varied from chondrite to chondrite and across particle types. Further results and details of the algorithms will be presented at the workshop. Future directions: Machine learning has the potential to revolutionize our understanding of complex particle populations contained within primitive astromaterial, with segmentation being a critical first step. Example applications include better understanding of particle transport, nebular reservoirs, parent body accretion, and a deeper understanding of the relationships between particle populations and bulk rock elemental and isotopic compositions. In addition to benefits that machine learning can bring to individual researchers, building a community data repository of thousands to millions of particles across hundreds of samples will open up many other possibilities. For example, with a large enough dataset it will be possible to search for exceptionally closely matching particles across disparate samples. Such a capability would enable a single CAI from OSIRISREx or Hayabusa/II samples to be matched to chondritic CAIs that exhibit near-identical size, texture, and mineralogy, down to the level of similar core phenocrysts, zonation, and rim sequences. Such comparative analyses will help to disentangle precursor chemistry, chronology, gas/dust reservoirs during heating, and accretion. Such an endeavor would be impossible without machine learning and a large community data repository of astromaterial chemical/mineralogic maps.

Machine Learning↗

Material transport in laser-heated diamond anvil cell melting experiments

A previously undocumented effect in the laser-heated diamond anvil cell, namely, the transport of molten species through the sample chamber, over distances large compared to the laser beam diameter, is presented. This effect is exploited to determine the melting behavior of high-pressure silicate assemblages of olivine composition. At pressures where beta-spinel is the phase melted, relative strengths of partitioning can be estimated for the incompatible elements studied. Iron was found to partition into the melt from beta-spinel less strongly than calcium, and slightly more strongly than manganese. At higher pressures, where a silicate perovskite/magnesiowuestite assemblage is melted, it is determined that silicate perovskite is the liquidus phase, with iron-rich magnesiowuestite accumulating at the end of the laser-melted stripe.

Campbell, Andrew J.↗

Thermal Expansion Coefficients of Ca2Y8(SiO4)6O2 and Ca2Yb8(SiO4)6O2 Apatite-type Silicates

High temperature X-ray diffraction (XRD) scans of Y2Si2O7 and Yb2Si2O7 reactions with calcium-magnesium-aluminosilicates (CMAS) were utilized to determine thermal expansion coefficients (CTEs) of Ca2Y8(SiO4)6O2 and Ca2Yb8(SiO4)6O2 apatite materials. In order to validate these measurements, the CTEs of Y2Si2O7, Yb2Si2O7 and SiO2 were also determined from the same scans. The directional CTEs for γ-Y2Si2O7 were determined to be αa=5.84×10-6/K, αb=6.81×10-6/K and αc=0.81×10-6/K, and β-Yb2Si2O7 was determined to have values of αa=6.89×10-6/K, αb=4.81×10-6/K and αc=2.78×10-6/K. The average CTEs of γ-Y2Si2O7 and β-Yb2Si2O7 were determined to be 4.5×10-6/K and 4.7×10-6/K, respectively, which agreed with previous analyses. Ca2Y8(SiO4)6O2 exhibited directional CTEs of αa=9.36×10-6/K and αc=7.95×10-6/K (averaged between two sets of data), whereas Ca2Yb8(SiO4)6O2 had values that were very similar (αa=9.63×10-6/K, αc=7.45×10-6/K). Both results for the Ca2RE8(SiO4)6O2 apatites correlated well with the limited data on apatite-type silicates available in literature.

rare earth↗

New constraints on Precambrian ocean composition

The Precambrian record of carbonate and evaporite sedimentation is equivocal. In contrast to most previous interpretations, it is possible that Archean, Paleoproterozoic, and to a lesser extent, Meso to Neoproterozoic seawater favored surplus abiotic carbonate precipitation, as aragonite and (hi-Mg?) calcite, in comparison to younger times. Furthermore, gypsum/anhydrite may have been only rarely precipitated prior to halite precipitation during evaporation prior to about 1.8 Ga. Two effects may have contributed to these relationships. First, sulfate concentration of seawater may have been critically low prior to about 1.9 Ga so the product mCa++ x mSO4-- would not have produced gypsum before halite, as in the Mesoproterozoic to modern ocean. Second, the bicarbonate to calcium ratio was sufficiently high so that during progressive evaporation of seawater, calcium would have been exhausted before the gypsum field was reached. The pH of the Archean and Paleoproterozoic ocean need not have been significantly different from the modern value of 8.1, even at CO2 partial pressures of a tenth of an atmosphere. Higher CO2 partial pressures require somewhat lower pH values.

NASA Discipline Exobiology↗

Gamma-spectrometric analysis of Luna 16 sample of lunar surface material

Using a scintillation gamma spectrometer with shielding against anticoincidences, the content of the natural radioelements (K, U, and Th) and long-lived cosmogenic radioisotopes (Al-26, Na-22, and Mn-54) in a sample of Sea of Fertility regolith was determined. Based on the content data of natural radioelements, an attempt was made to classify this sample in the scale of petrochemical types of terrestrial rocks arranged in accordance with their silicic content and alkalinity. Within the frame of reference of calcium-uranium systematics of lunar samples, a comparison was made of the K/U ratio obtained for the Sea of Fertility sample with analogous data for other regions of the moon. Also discussed are problems on the depthwise distribution of cosmogenic radioisotopes along the regolith profile.

Surkov, Y. A.↗

Reactivity of Calcium-Bearing Minerals Under Simulated Venus Conditions

•SO2 is reactive with several common elements e.g. calcium [1-4] •Knowledge on chemical reactions has implications for the past and current state of Venus - Venus may have had liquid water on its surface [5], thus hydrous silicates may have formed at that time [6]. - The Venus Emissivity Mapper (on VERITAS and EnVision) will be used to determine bulk composition of the surface by observing transition metal content [8-9] - Calcium diffuses through basalt to react with CO2 and SO2, changing the bulk composition and decreasing the emissivity from orbit [8] - Experiments investigating kinetics will be informative for future emissivity data •Goal: - Constrain reaction rate between several calcium minerals and SO2 - Determine the effect, if any, crystal lattices may have on these rates

S.T. Port↗

Phosphates in pallasite meteorites as probes of mantle processes in small planetary bodies

Trace element analyses of the phosphates minerals in stony-iron pallasite meteorites are used here to investigate the magmatic history of the silicate portions of pallasites. In Eagle Station and seven other pallasites, the phosphates have relatively low concentrations of REEs and are strongly enriched in heavy relative to light REE. These patterns are consistent with formation of phosphate by subsolidus reactions between metal and silicate, in which phosphate inherits the REE pattern of olivine. In Springwater and Santa Rosalia, calcium-rich phosphates have higher concentrations of REE, are enriched in light relative to heavy REE, and have negative europium anomalies. These patterns are consistent with crystallization of phosphate from a europium-depleted chondritic liquid. This is unlikely to have happened near the base of the differentiating parent-body mantle; it suggests that some pallasites may come from regions of their parent bodies much nearer the surface than the core-mantle boundary.

Davis, Andrew M.↗

Olivine and Pyroxene Compositions in Fine-Grained Chondritic Materials

Our analyses of the Wild-2 samples returned by the Stardust Mission have illuminated critical gaps in our understanding of related astromaterials. There is a very large database of olivine and low-calcium pyroxene compositions for coarse-grained components of chondrites, but a sparse database for anhydrous silicate matrix phases. In an accompanying figure, we present comparisons of Wild-2 olivine with the available chondrite matrix olivine major element data. We thus have begun a long-term project measuring minor as well as major element compositions for chondrite matrix and chondritic IDPs, and Wild 2 grains. Finally, we wish to re-investigate the changes to fine-grained olivine and low-Ca pyroxene composition with progressive thermal metamorphism. We have examined the LL3-4 chondrites which because of the Hayabusa Mission have become very interesting.

Zolensky, Michael E.↗

Less-Altered CI Lithology in the Kaidun Meteorite Breccia

One of the most interesting initial results of the characterization of the asteroid Ryugu regolith material returned by the Hayabusa2 spacecraft is the presence of a significant quantity of less-aqueously altered CI material, tentatively called “CI2”. This lithology is characterized by an approximately ten-fold increase in the amount of an hydrous ferromagnesian silicates over what is found n CI1 chondrites, with these being principally olivine, low- and high-calcium pyroxene. Remnant CAI phases are found as well as probable chondrule fragments. Magnetite, pyrrhotite and hydroxyapatite are abundant. The main carbonate is calcite. Matrix is mainly a mixture of saponite and serpentine phases. Assuming that this lithology should be a better representative of the more “primordial” mineralogy of early nebular solids than more processed CI1 material, we have been re-examining CI lithologies found as separate meteorites as well as clasts in other meteorites, seeking similar CI2 material. The Kaidun breccia is notorious for including almost every type of meteorite class except CR2 (which is ironic considering that Kaidun is still officially classified as CR2). We report here the discovery of a probable CI2 lithology in one carbonaceous chondrite-rich Kaidun sample.

Michael Zolensky↗

"CHON" particles: The interstellar component of cometary dust

Interstellar dust is characterized by strong absorption in the ultraviolet and the mid-IR. Current models of interstellar dust are based on three chemically distinct components: a form of carbon (usually graphite), a silicate, and a blend of polycyclic aromatic hydrocarbons or other carbonaceous material. Previous work using effective medium theories to understand the optical properties of cometary dust suggested that an amalgam of materials could reproduce the observed interstellar and cometary dust features. Recently, Lawler and Brownlee (1992) re-analyzed the PIA and PUMA-1 data sets from the Giotto flyby of P/Halley and discovered that the so-called "CHON" particles were actually composed of a blend of carbon-bearing and silicon-bearing materials. Based on effective medium theories, the absorption spectrum of such a material would display the spectral features of each of the components - strong UV absorption from the carbonaceous component and strong absorption in the IR from the silicate component. To test this idea, vapor-deposited samples were created using two different deposition techniques: sputtering with an argon RF magnetron and deposition from an argon plasma torch. Two different compositions were tested: a blend of graphite and silica in a 7:1 ratio and an amalgam of materials whose approximate composition matches the "CHON"-silicate abundances for the uncompressed PIA data set of Lawler and Brownlee: graphite, iron oxide, magnesium oxide, ammonium sulfate, calcium carbonate, and silica in mass ratios of 6:4.3:4:2.2:1:9. The samples were finely ground and pressed into 2" diameter disks using a 40 ton press. In all, four different experiments were performed: one with each of the compositions (C:SiO and "CHON") in both the RF magnetron and the plasma torch chambers. The RF magnetron created a uniform dark thin film on the substrate surface, and the plasma torch created a coating of small (<100 micron) diameter grey particles. The spectra of all four samples show a strong, broad absorption feature at around 220 nm as well as a strong but narrower absorption peak near 10 microns. The RF magnetron sputtered samples showed some sub-structure in the UV, and the peak of the absorption was shifted toward longer wavelengths. The UV absorption in the plasma torch deposited samples have no sub-structure, and the peak absorption is very near 220 nm. Strong absorption near 9 microns is seen in the spectra from both sample preparation techniques, and is consistent with the IR spectra of some terrestrial silicates. Other features, particularly at 6.2 and 8.6 microns, are seen in the interstellar medium. A strong feature near 2 microns is due to absorbed water in the sample. Based on the results of these experiments, there is evidence that a material with a composition similar to that detected in "CHON" particles in the coma of P/Halley have a spectral signature which reproduces the main absorption features of interstellar dust. This suggests that the "CHON" particles could be the interstellar component of cometary dust.

Lien, David J.↗

Reflectance and Thermal Infrared Spectroscopy of Mars: Relationship Between ISM and TES for Compositional Determinations

Reflectance spectroscopy has demonstrated that high albedo surfaces on Mars contain heavily altered materials with some component of hematite, poorly crystalline ferric oxides, and an undefined silicate matrix. The spectral properties of many low albedo regions indicate crystalline basalts containing both low and high calcium pyroxene, a mineralogy consistent with the basaltic SNC meteorites. The Thermal Emission Spectrometer (TES) experiment on the Mars Geochemical Surveyor has acquired critical new data relevant to surface composition and mineralogy, but in a wavelength region that is complementary to reflectance spectroscopy. The essence of the completed research was to analyze TES data in the context of reflectance data obtained by the French ISM imaging spectrometer experiment in 1989. This approach increased our understanding of the complementary nature of these wavelength regions for mineralogic determinations using actual observations of the martian surface. The research effort focused on three regions of scientific importance: Syrtis Major-Isidis Basin, Oxia Palus-Arabia, and Valles Marineris. In each region distinct spatial variations related to reflectance, and in derived mineralogic information and interpreted compositional units were analyzed. In addition, specific science questions related to the composition of volcanics and crustal evolution, soil compositions and pedogenic processes, and the relationship between pristine lithologies and weathering provided an overall science-driven framework for the work. The detailed work plan involved colocation of TES and ISM data, extraction of reflectance and emissivity spectra from areas of known reflectance variability, and quantitative analysis using factor analysis and statistical techniques to determine the degree of correspondence between these different wavelength regions. Identified coherent variations in TES spectroscopy were assessed against known atmospheric effects to validate that the variations are due to surface properties. With this new understanding of reflectance and emission spectroscopy, mineralogic interpretations were derived and applied to the science objectives of the three regions.

Boyce, Joseph↗

Melting relations of the Allende meteorite

The proportions of major oxides in the Allende carbonaceous chondrite after partial reduction are remarkably similar to those in possible mantle material of the earth. When heated, the Allende meteorite generates a sulfide melt, a ferrobasaltic melt, and olivine with or without pyroxene, over a wide pressure range (5 to 25 kilobar). The silicate melt contains more sodium and less titanium than lunar ferrobasalts. An aggregate of the Allende chondrite rich in calcium and aluminum produces silica-undersaturated, calcium-rich melt and spinel over a wide pressure and temperature range. It is suggested that the earth's core contains significant amounts of both nickel and sulfur and that a 3:2 mixture of Allende bulk sample and calcium- and aluminum-rich agregates is closer in major element abundances than either of these components to the average composition of the moon.

Seitz, M. G.↗

Mineralogy and Petrology of EK-459-5-1, A Type B1 CAI from Allende

Calcium-aluminum-rich inclusions (CAIs) are a type of coarse-grained clast composed of Ca-, Al-, and Mg-rich silicates and oxides found in chondrite meteorites. Type B (CAIs) are exclusively found in the CV chondrite meteorites and are the most well studied type of inclusion found in chondritic meteorites. Type B1 CAIs are distinguished by a nearly monomineralic rim of melilite that surrounds an interior predominantly composed of melilite, fassaite (Ti and Al-rich clinopyroxene), anorthite, and spinel with varying amounts of other minor primary and secondary phases. The formation of Type B CAIs has received considerable attention in the course of CAI research and quantitative models, experimental results and observations from Type B inclusions remain largely in disagreement. Recent experimental results and quantitative models have shown that the formation of B1 mantles could have occurred by the evaporative loss of Si and Mg during the crystallization of these objects. However, comparative studies suggest that the lower bulk SiO2 compositions in B1s result in more prior melilite crystallization before the onset of fassaite and anorthite crystallization leading to the formation of thick melilite rich rims in B1 inclusions. Detailed petrographic and cosmochemical studies of these inclusions will further our understanding of these complex objects.

Jeffcoat, C. R.↗

Mineralogy of the Almahata Sitta Ureilite

Mineralogy & Petrography: Almahata Sitta, deriving from the asteroid 2008 TC3, is a coarse-grained- to porous, fine-grained, fragmental breccia with subrounded mineral fragments and olivine aggregates embedded in a cataclastic matrix of ureilitic material. Mineral fragments include polycrystalline olivine, low-calcium, pigeonite, and augite. Abundant carbonaceous aggregates containing graphite, microdiamonds and aliphatics. Kamacite, Cr-rich troilite, silica and schreibersite are abundant. The compositional range of the silicates is characteristic of the ureilites as a group, but unusually broad for an individual ureilite. The dense lithology is typical for ureilites, but the porous lithology is anomalous. In the porous lithology pore walls are largely coated by crystals of olivine. Classification: Almahata Sitta is an anomalous, polymict eucrite. Anomalous features include large compositional range of silicates, high abundance and large size of pores, crystalline pore wall linings, and fine-grained texture. Tomography reveals that the pores define thin, discontinuous "sheets" connected in three dimensions, suggesting that they outline grains that have been incompletely welded together. The crystals lining the pore walls are probably vapor phase deposits. Therefore Almahata Sitta may represent an agglomeration of coarse- to fine-grained, incompletely reduced pellets formed during impact, and subsequently welded together at high temperature.

Zolensky, Michael E.↗

Calcium-Magnesium-Aluminosilicate (CMAS) Reactions and Degradation Mechanisms of Advanced Environmental Barrier Coatings

The thermochemical reactions between calcium-magnesium-aluminosilicate- (CMAS-) based road sand and several advanced turbine engine environmental barrier coating (EBC) materials were studied. The phase stability, reaction kinetics and degradation mechanisms of rare earth (RE)-silicates Yb2SiO5, Y2Si2O7, and RE-oxide doped HfO2 and ZrO2 under the CMAS infiltration condition at 1500 C were investigated, and the microstructure and phase characteristics of CMAS-EBC specimens were examined using Scanning Electron Microscopy (SEM) and X-ray Diffraction (XRD). Experimental results showed that the CMAS dissolved RE-silicates to form crystalline, highly non-stoichiometric apatite phases, and in particular attacking the silicate grain boundaries. Cross-section images show that the CMAS reacted with specimens and deeply penetrated into the EBC grain boundaries and formed extensive low-melting eutectic phases, causing grain boundary recession with increasing testing time in the silicate materials. The preliminary results also showed that CMAS reactions also formed low melting grain boundary phases in the higher concentration RE-oxide doped HfO2 systems. The effect of the test temperature on CMAS reactions of the EBC materials will also be discussed. The faster diffusion exhibited by apatite and RE-doped oxide phases and the formation of extensive grain boundary low-melting phases may limit the CMAS resistance of some of the environmental barrier coatings at high temperatures.

Ahlborg, Nadia L.↗

Joint M3 and Diviner Analysis of the Mineralogy, Glass Composition, and Country Rock Content of Pyroclastic Deposits in Oppenheimer Crater

Here we present our analysis of the near- and mid-infrared spectral properties of pyroclastic deposits within the floor fractured Oppenheimer Crater that are hypothesized to be Vulcanian in origin. These are the first results of our global study of lunar pyroclastic deposits aimed at constraining the range of eruption processes on the Moon. In the near-infrared, we have employed a new method of spectral analysis developed in Horgan et al. (2013) of the 1 m iron absorption band in Chandrayaan-1 Moon Mineralogy Mapper (M3) spectra. By analyzing both the position and shape of the 1 m band we can detect and map the distribution of minerals, glasses, and mixtures of these phases in pyroclastic deposits. We are also using mid-infrared spectra from the Lunar Reconnaissance Orbiter Diviner Lunar Radiometer Experiment to develop ~200 m/pixel Christiansen Feature (CF) maps, which correlate with silica abundance. One of the benefits of using CF maps for analysis of pyroclastic deposits is that they can be used to detect silicic country rock that may have been emplaced by Vulcanian-style eruptions, and are sensitive to iron abundance in glasses, neither of which is possible in the near-infrared. M3 analysis reveals that the primary spectral endmembers are low-calcium pyroxene and iron-bearing glass, with only minor high-calcium pyroxene, and no detectable olivine. The large deposit in the south shows higher and more extensive glass concentrations than the surrounding deposits. We interpret the M3 spectra of the pyroclastic deposits as indicating a mixture of low-calcium pyroxene country rock and juvenile glass, and no significant olivine. Analysis of Diviner CF maps of the Oppenheimer crater floor indicates an average CF value of 8.16, consistent with a mixture of primarily plagioclase and some pyroxene. The average CF values of the pyroclastic deposits range from 8.31 in the SW to 8.24 in the SE. Since CF values within the deposits are as high as 8.49, the lower average CF values of the deposits suggest that each deposit is a mixture of crater floor material and highly mafic juvenile material consistent with either olivine or Fe-bearing pyroclastic glass. Synthesizing our M3 and Diviner results indicates that the crater floor consists of plagioclase with some pyroxene, and the pyroclastic deposits are a mix of this substrate and a glass-rich juvenile material. While we cannot determine the iron content of the glass from M3 spectra alone, the high Diviner CF values suggest that the glass is relatively iron-rich. Indeed, FeO abundances inferred from CF values using the method of Allen et al. (2012) imply that the large southern deposit exhibits a significant enhancement in iron content. This supports our hypothesis that the glass in this deposit is relatively iron-rich.

Bennett, Kristen A.↗

Preliminary results from the Viking X-ray fluorescence experiment - The first sample from Chryse Planitia, Mars

Iron, calcium, aluminum, silicon, and sulfur are major elements in the first surface sample of Mars that has been analyzed by the Viking X-ray fluorescence spectrometer. Titanium is present in minor quantities. This is consistent with the sample's being a mixture of fine silicate and oxide mineral grains, with a significant proportion of sulfates, possibly hydrated. Ferric oxide is regarded as the red pigmenting agent on the Martian surface, but if it coats silicate grains, the coatings must be very thin or discontinuous. A high abundance of Fe, relatively low abundances of Al, Rb, Sr, and Zr, and a high Ca/K ratio are distinctive features of the spectra. Preliminary determinations indicate the following abundances (as percentages by weight): Fe, 14 plus or minus 2; Ti, less than 1; S, 2 to 5; the Ca/K ratio by weight is greater than 5.

Toulmin, P., III↗