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X-ray Mapping of Terrestrial and Extraterrestrial Materials Using the Electron Microprobe

Lunar samples returned from the Apollo program motivated development of the Bence-Albee algorithm for the rapid and accurate analysis of lunar materials, and established interlaboratory comparability through its common use. In the analysis of mineral and rock fragments it became necessary to combine micro- and macroscopic analysis by coupling electron-probe microanalysis (EPMA) with automated stage point counting. A coarse grid that included several thousand points was used, and initially wavelength-dispersive (WDS) and later energydispersive (EDS) data were acquired at discrete stage points using approx. 5 sec count times. A approx 50 micrometer beam diameter was used for WDS and up to 500 micrometer beam diameter for EDS analysis. Average analyses of discretely sampled phases were coupled with the point count data to calculate the bulk composition using matrix algebra. Use of a defocused beam resulted in a contribution from multiple phases to each analytical point, and the analytical data were deconvolved relative to end-member phase chemistry on the fly. Impressive agreement was obtained between WDS and EDS measurements as well as comparison with bulk chemistry obtained by other methods. In the 30 years since these methods were developed, significant improvements in EPMA automation and computer processing have taken place. Digital beam control allows routine collection of x-ray maps by EDS, and stage mapping for WDS is conducted continuously at slew speed and incrementally by sampling at discrete points. Digital pulse processing in EDS systems has significantly increased the throughput for EDS mapping, and the ongoing development of Si-drift detector systems promises mapping capabilities rivaling WDS systems. Spectrum imaging allows a data cube of EDS spectra to be acquired and sophisticated processing of the original data is possible using matrix algebra techniques. The study of lunar and meteoritic materials includes the need to conveniently: (1) Characterize the sample at microscopic and macroscopic scales with relatively high sensitivity, (2) Determine the modal abundance of minerals, and (3) Identify and relocate discrete features of interest in terms of size and chemistry. The coupled substitution of cations in minerals can result in significant variation in mineral chemistry, but at similar average Z, leading to poor backscattered-electron (BSE) contrast discrimination of mineralogy. It is necessary to discriminate phase chemistry at both the trace element level and the major element level. To date, the WDS of microprobe systems is preferred for mapping due to high throughput and the ability to obtain the necessary intensity to discriminate phases at both trace and major element concentrations. It is desirable to produce fully quantitative compositional maps of geological materials, which requires the acquisition of k-ratio maps that are background and dead-time corrected, and which have been corrected by phi(delta z> or an equivalent algorithm at each pixel. To date, turnkey systems do not allow the acquisition of k-ratio maps and the rigorous correction in this manner. X-ray maps of a chondrule from the Ourique meteorite, and a comb-layered xenolith from the San Francisco volcanic field, have been analyzed and processed to extract phase information. The Ourique meteorite presents a challenge due to relatively low BSE contrast, and has been studied using spectrum imaging. X-ray maps for Si, Mg, and FeK(alpha) were used to produce RGB images. The xenolith sample contains sector-zoned augite, olivine, plagioclase, and basaltic glass. X-ray maps were processed using Lispix and ImageJ software to produce mineral phase maps. The x-ray maps for Mg, Ca, and Ti were used with traceback to generate binary images that were converted to RGB images. These approaches are successful in discriminating phases, but it is desirable to achieve the methods that were used on lunar samples 30 years ago on current microprobe systems. Curnt research includes x-ray mapping analysis of the Dalgety Downs chondrite by micro x-ray fluorescence and spectrum imaging, in collaboration with Kenny Witherspoon of IXRF Systems and Dale Newbury of NIST.

Carpenter, P.↗

Integrated Bio-ISRU and Life Support Systems at the Lunar Outpost: Concept and Preliminary Results

We continue the development of our concept of a biotechnological loop for in-situ resource extraction along with propellant and food production at a future lunar outpost, based on the cultivation of litholytic cyanobacteria (LCB) with lunar regolith (LR) in a geobioreactor energized by sunlight. Our preliminary studies have shown that phototropic cultivation of LCB with simulants of LR in a low-mineralized medium supplemented with CO2 leads to rock dissolution (bioweathering) with the resulting accumulation of Fe, Mg and Al in cyanobacterial cells and in the medium. LCB cultivated with LR simulants produces more O2 than the same organisms cultivated in a high-mineralized medium. The loss of rock mass after bioweathering with LCB suggests the release of O from regolith. Further studies of chemical pathways of released O are required. The bioweathering process is limited by the availability of CO2, N, and P. Since lunar regolith is mainly composed of O, Si, Ca, Al and Mg, we propose to use organic waste to supply a geobioreactor with C, N and P. The recycling of organic waste, including urine, through a geobioreactor will allow for efficient element extraction as well as oxygen and biomass production. The most critical conclusion is that a biological life support system tied to a geobioreactor might be more efficient for supporting an extraterrestrial outpost than a closed environmental system.

Brown, I. I.↗

The Effects of Clumping on Wind Line Variability

We review the effects of clumping on the profiles of resonance doublets. By allowing the ratio of the doublet oscillator strengths to be a free parameter, we demonstrate that doublet profiles contain more information than is normally utilized. In clumped (or porous) winds, this ratio can lie between unity and the ratio of the f-values, and can change as a function of velocity and time, depending on the fraction of the stellar disk that is covered by material moving at a particular velocity at a given moment. Using these insights, we present the results of SEI modeling of a sample of B supergiants, sigma Pup and a time series for a star whose terminal velocity is low enough to make the components of its Si VI lambda lambda 1400 independent. These results are interpreted within the framework of the Oskinova et al. (2007) model, and demonstrate how the doublet profiles can be used to extract information about wind structure.

Prinja, R. K.↗

Allochthonous Addition of Meteoritic Organics to the Lunar Regolith

Preparation of lunar samples 74220,861 was discussed in detail in [3, 4]. Our analysis sequence was as follows: optical microscopy, UV fluorescence imaging, -Raman, FESEM-EDX imaging and mapping, FETEMEDX imaging and mapping of a Focused Ion Beam (FIB) extracted section, and NanoSIMs analysis. We observed fluffytextured C-rich regions of interest (ROI) on three different volcanic glass beads. Each ROI was several m2 in size and fluoresced when exposed to UV. Using FESEM/EDX, the largest ROI measured ~36 m and was located on an edge of a plateau located on the uppermost surface of the bead. The ROI was covered on one edge by a siliceous filament emanating from the plateau surface indicating it was attached to the bead while on the Moon. EDX mapping of the ROI shows it is composed primarily of heterogeneously distributed C. Embedded with the carbonaceous phase are localized concentrations of Si, Fe, Al and Ti indicating the presence of glass and/or minerals grains. -Raman showed strong D- and G-bands and their associated second order bands; intensity and location of these bands indicates the carbonaceous matter is structurally disorganized. A TEM thin section was extracted from the surface of a glass bead using FIB microscopy. High resolution TEM imaging and selected area electron diffraction demonstrate the carbonaceous layer to be amorphous; it lacked any long or short range order characteristic of micro- or nanocrystalline graphite. Additionally TEM imaging also revealed the presence of submicron mineral grains, typically < 50 nm in size, dispersed within the carbonaceous layer. NanoSIMs data will be presented and discussed at the meeting. Given the noted similarities between the carbonaceous matter present on 74220 glass beads and meteoritic kerogen, we suggest the allochthonous addition of meteoritic organics as the most probable source for the C-rich ROIs.

Thomas-Keprta, K. L.↗

Separating Silicon From Si/NaF Mixtures

New method of extracting silicon from mixture produced when silicon tetrafluoride is reduced by sodium takes advantage of lower melting point of NaF. Method is effective at temperatures up to 400 degrees C below melting point of Si. Results in energy and economic savings: simpler and smaller furnaces, less volatization loss, and high percentage of separation.

Sanjurjo, A.↗

Bringing Thunder and Lightning Indoors

Piezoelectric materials convert mechanical energy into electrical energy and electrical energy into mechanical energy. They generate electrical charges in response to mechanical stress and generate mechanical displacement and/or force when subjected to an electric current. Scientists at Langley Research Center have developed a piezoelectric device that is superior in many ways to those that used to be the only ones commercially available. It is tougher, has far greater displacement and greater mechanical load capacity for a comparative voltage operation, can be easily produced at a relatively low cost, and lends itself well to mass production. The NASA-developed piezoelectric device is also unique in that it is more efficient in extracting electrical energy from the mechanical energy that goes in. It works on a simple principle. A thin ceramic piezoelectric wafer is sandwiched between an aluminum sheet and a steel sheet and held together with LaRC-SI, an amorphous thermoplastic adhesive with special properties created by NASA at Langley. The sandwich is heated in an autoclave, and the adhesive melts. When the sandwich cools, the adhesive bonds the parts together into one piezoelectric element. While they cool, the components of the element contract at different rates, since they are made of different materials. This differential shrinkage causes the element to warp in either a convex or concave shape, depending on which way it is oriented. The shrinking of the outside metal layers places the inside piezoelectric ceramic under mechanical stress. If the element is cantilevered by clamping one side and then plucked, it reverberates like a diving board that has just ejected a diver. This way, a small amount of mechanical energy can result in a relatively long period of electrical generation. When the piezoelectric element is used for the creation of electricity, it is called Lightning. This same sandwiched piezoelectric wafer can also convert electrical energy into mechanical energy. Then, it is called Thunder. Electricity goes in, excites the element, and then, mechanical energy in the form of movement is generated.

Source record↗

Harnessing surface plasmons for solar energy conversion

NASA research on the feasibility of solar-energy conversion using surface plasmons is reviewed, with a focus on inelastic-tunnel-diode techniques for power extraction. The need for more efficient solar converters for planned space missions is indicated, and it is shown that a device with 50-percent efficiency could cost up to 40 times as much per sq cm as current Si cells and still be competitive. The parallel-processing approach using broadband carriers and tunable diodes is explained, and the physics of surface plasmons on metal surfaces is outlined. Technical problems being addressed include phase-matching sunlight to surface plasmons, minimizing ohmic losses and reradiation in energy transport, coupling into the tunnels by mode conversion, and gaining an understanding of the tunnel-diode energy-conversion process. Diagrams illustrating the design concepts are provided.

Anderson, L. M.↗

Solar Cells for Lunar Application

In this work a preliminary study of the vacuum evaporation of silicon extracted from the lunar regolith has been undertaken. An electron gun vacuum evaporation system has been adapted for this purpose. Following the calibration of the system using ultra high purity silicon deposited on Al coated glass substrates, thin films of lunar Si were evaporated on a variety of crystalline substrates as well as on glass and lightweight 1 mil (25 microns) Al foil. Extremely smooth and featureless films with essentially semiconducting properties were obtained. Optical absorption analysis sets the bandgap (about 1.1 eV) and the refractive index (n=3.5) of the deposited thin films close to that of crystalline silicon. Secondary ion mass spectroscopy and energy dispersive spectroscopy analysis indicated that these films are essentially comparable to high purity silicon and that the evaporation process resulted in a substantial reduction of impurity levels. All layers exhibited a p-type conductivity suggesting the presence of a p-type dopant in the fabricated layers. While the purity of the 'lunar waste material' is below that of the 'microelectronic-grade silicon', the vacuum evaporated material properties seems to be adequate for the fabrication of average performance Si-based devices such as thin film solar cells. Taking into account solar cell thickness requirements (greater than 10 microns) and the small quantities of lunar material available for this study, solar cell fabrication was not possible. However, the high quality of the optical and electronic properties of evaporated thin films was found to be similar to those obtained using ultra-high purity silicon suggest that thin film solar cell production on the lunar surface with in situ resource utilization may be a viable approach for electric power generation on the moon.

Freundlich, Alex↗

Understanding the Space Weathering of Mercury Through Laboratory Experiments

Introduction: Airless surfaces across the solar system are continually modified by energetic particles from solar wind and micrometeoroid bombardment [1,2]. This process is known as space weathering, and it alters the chemical, microstructural, and optical properties of surface regoliths on airless bodies, including Mercury. On the Moon and S-type asteroids, the reflectance spectral signatures of space weathering include reddening (increasing reflectance with increasing wavelength), darkening (lowering of reflectance), and the attenuation of characteristic absorption bands [2]. Such spectral changes are driven by the production of Fe-bearing nanoparticles(npFe) through both solar wind irradiation and micrometeoroid bombardment. While our understanding of space weathering for the Moon and near-Earth S-types asteroids is advanced, insight into how these processes operate on other planetary bodies is limited. In particular, Mercury experiences a uniquely intense space weathering environment than planetary counterparts at 1 AU, including a moreintense solar wind flux and higher velocity micrometeoroid impacts [4]. Additionally, Mercury has a surface composition unique in the inner solar system, including regions of the surface with very low albedo known as the low reflectance material (LRM), which is enriched in carbon, likely graphite, up to 4wt.% [5].In addition, the concentration of Fe across Mercury’s surface islow (<2 wt.%) compared to the Moonor S-type asteroids asteroids[6]. Our understanding of the effects of space weathering on C-rich and Fe-poor phases is limited. Since Fe plays a critical role inthe development of space weathering characteristicson other airless surfaces(e.g., npFe), its limited availability may significantly affect the development of space weathering features in Mercury surface materials. We can simulate space weathering processes in the laboratory to explore their effects on the microstructural, chemical, and spectral characteristics of Mercury surface materials[7]. Here we used pulsed laser irradiation to simulate the short duration, high-temperature events associated with micrometeoroid impacts. We performed coordinated analyses including reflectance spectroscopy and electron microscopy to investigate the spectral, chemical, and microstructural changes in these mercurian analog samples. Methods: For these experiments, we usedforsteritic olivine with varying FeOcontents, a mineral phase proposed to be abundant on the surface of Mercury. We mixed each sample with graphite to simulate LRM regions of the surface. Wesynthesized the olivinesamplesat 1-bar at NASA’s Johnson Space Centerand prepared pressed powder pellets for laser irradiation [8].We prepared three samples, each with a base layer of olivineto maintain structural integrity and topped witha surface layer containing the graphite-olivine mixture: 1) Sample SC-001 San Carlos olivine(Fo90.91),2)Sample F-S-002 with0.05 wt.% FeO olivine, and 3) F-T-004 with 0.53 wt.% FeO olivine. Each sample was mixed with 5 wt.% powdered graphite and had grain sizes ranging from 45to 125μm. We irradiated each sample usinga pulsed Nd-YAG laser, (l=1064 nm, ~6 ns pulse duration, energy of 48 mJ/pulse) while undervacuumat Northern Arizona University. The laser was rastered1x and then 5x over the surfaceof each sample to simulate progressive space weathering. We collected in situreflectance spectra from the samples after each laser pulse witha Nicolet IS50 Fourier-Transform Infrared spectrometer (lfrom 0.65-2.5 μm). We used an FEI Nova NanoSEM200scanning electron microscope (SEM) and a Hitachi TM4000 Plus benchtop SEM at Purdue University to image the surface morphology and topography of the samples. We extracted thin sections for analysis in the transmission electron microscope(TEM)using the FEI Helios NanoLab 660 focused ion beam (FIB) SEM at the University of Arizona.We performed analysis of the microstructural and chemical characteristics of the samples using the 200 keV JEOL 2500 scanning TEM at Johnson Space Center. Reflectance Spectroscopy Results:Reflectance spectra for each sample are shown in Fig. 1.SC-001:The spectrum of the unirradiated sample exhibits a weak 1.0 μm absorption feature, associated with Fe2+in the olivine,and low overall reflectance (Fig. 1a). Thereflectance and the depth of the absorption band increases after 1x laser raster but are at their lowest after 5x laser rasters.F-T-004:The unirradiated sample has a blue-sloped spectrum with low reflectance without identifiable absorption features (Fig. 1b). With progressive laser irradiation, the sample reflectance increases and becomes strongly red-sloped.F-S-002:The unirradiated sample exhibits a dark, blue-slopedspectrum. The brightness of the sample increases significantly from <0.2average reflectance over >0.8 reflectance in the most irradiated sampleand thespectral slope also becomesslightly reddened (Fig. 1c). Microstructural and Chemical Analysis: Two primary alteration textures were observed in the samples exposed to simulated space weathering: 1) fluffy C-rich,and 2) vesiculated melt. The fluffy C-rich texture is composed oflow-densitydeposits distributed across the surface of the sample(Fig. 2A). Analysis of a FIB section extracted from a low-density C-rich region in sample SC-001 reveals multiple globule-type deposits, discrete from stacked graphite, likely produced via melting from the laser irradiation [9].The vesiculated melt textureis smooth and uniformly distributed across isolated regions of the sample surface. The vesicles measure up to 100s of nmin diameter. Analysis of a FIB section from this texture was extracted from sample F-T-004 reveals a layer of amorphous melt material, close to 100 nm thick and uniform across the FIB section (Fig. 2B). Isolated regions of this melt layer contain small nanoparticles, <5 nm in diameter. Chemical analysis through energy dispersive X-ray spectroscopy reveals the composition of this layer is enriched in Si and depleted in Mg and O compared to the underlying sample. Implications for Space Weathering on Mercury: Previous experiments simulating space weathering of Mercury have showndarkening and reddening of spectra[7,10].However, our use of low-Fe materials and graphite to create a sample set more analogous to the mercurian surface. Our results indicate that sample composition plays a significant and important role in the space weathering of Mercury. In particular, our spectral data demonstrates a strong correlation between spectral slope, Fe content, and simulated space weathering. While the variation in FeO content between samples F-S-002 and F-T-004 is <0.6 wt.%, the spectra deviate from flat to strongly red-sloped(F-T-004). This reddeningmay be linked to the presence of very small nanoparticles observed in the melt textures extracted from sample F-T-004. For the SC-001 sample, the fluffy C-rich textures may be developed by the amalgamation of small graphite particles into these unique morphologies. Such observations indicate that space weathering on Mercury may result in both familiar and new microstructural and chemical characteristics. References: [1]Hapke B. (2001) J. Geophys. Res.-Planet.,106,10039–10073. [2]Pieters C.M. and Noble S.K. (2016) J. Geophys. Res-Planet., 121, 1865–1884. [3] Lucey P.G., and Riner, M.A. (2011) Icarus,212, 451-462.[4]CintalaM.J.(1992)J. Geophys. Res.-Planet.,97,947–973.[5]Klima R.L.et al.(2018)Geophys.Res.Letters, 45, 2945–2953. [6]Nittler L.R., et al. (2011) Science 333, 1847-1850.[7]Sasaki S. and Kurahashi E. (2004) Space weathering on Mercury, Adv.Space Res., 33, 2152-2155.[8] Vander KaadenK.E., et al. (2018) LPSCXLIX, Abstract 1230. [9] McGlaun M.L. et al. (2019) LPSCL, Abstract 2019. [10] TrangD.et al. (2018)LPSCXLIX,Abstract2083

M S Thompson↗

CFD Extraction Tool for TecPlot From DPLR Solutions

This invention is a TecPlot macro of a computer program in the TecPlot programming language that processes data from DPLR solutions in TecPlot format. DPLR (Data-Parallel Line Relaxation) is a NASA computational fluid dynamics (CFD) code, and TecPlot is a commercial CFD post-processing tool. The Tec- Plot data is in SI units (same as DPLR output). The invention converts the SI units into British units. The macro modifies the TecPlot data with unit conversions, and adds some extra calculations. After unit conversions, the macro cuts a slice, and adds vectors on the current plot for output format. The macro can also process surface solutions. Existing solutions use manual conversion and superposition. The conversion is complicated because it must be applied to a range of inter-related scalars and vectors to describe a 2D or 3D flow field. It processes the CFD solution to create superposition/comparison of scalars and vectors. The existing manual solution is cumbersome, open to errors, slow, and cannot be inserted into an automated process. This invention is quick and easy to use, and can be inserted into an automated data-processing algorithm.

Norman, David↗

Oxygen extraction from lunar soil by fluorination

Mining and processing of lunar material could possibly lead to more cost-efficient scenarios for permanent presence of man in space and on the Moon. Production of oxygen for use as propellant seems especially important. Different candidate processes for oxygen-extraction from lunar soil were proposed, of which the reduction of ilmenite by hydrogen was studied most. This process, however, needs the concentration of ilmenite from lunar regolith to a large extent and releases oxygen only with low efficiency. Another possibility - the fluorination method - which works with lunar bulk material as feedstock is discussed. Liberation of oxygen from silicate or oxide materials by fluorination methods has been applied in geoscience since the early sixties. The fact that even at moderate temperatures 98 to 100 percent yields can be attained, suggests that fluorination of lunar regolith could be an effective way of propellant production. Lunar soil contains about 50 percent oxygen by weight which is gained nearly completely through this process as O2 gas. The second-most element Si is liberated as gaseous SiF4. It could be used for production of Si-metal and fluorine-recycling. All other main elements of lunar soil will be converted into solid fluorides which also can be used for metal-production and fluorine-recycling. Preliminary results of small scale experiments with different materials are discussed, giving information on specific oxygen-yields and amounts of by-products as functions of temperature. These experiments were performed with an already existing fluorine extraction and collection device at the University of Bonn, normally used for determination of oxygen-isotopic abundances. Optimum conditions, especially concerning energy consumption, are investigated. Extrapolation of the experimental results to large industrial-type plants on the Moon is tried and seems to be promising at first sight. The recycling of the fluorine is, however, crucial for the process. It might be achieved by means of electrolysis. This needs further investigation. The technical problem of transport and handling of the toxic and corrosive fluorine seems to be solvable and could be done by inert storage vessels.

Seboldt, W.↗

The abundances of major elements in Cas A and Tycho supernova remnants

The objective of this program was to map the abundances of major elements such as O, Si, S, and Fe in the supernova remnants, Tycho and Cas A. The approach was based upon using archival cosmic X-ray data from several space missions, notably, the Einstein Observatory, EXOSAT, ROSAT, BBSRT, and ASCA. Two of the missions, Einstein and ROSAT, had high resolution telescopes that provided excellent images, but no spectral information. Two missions with much poorer resolution telescopes, BBXRT and ASCA, gave good spectral information through pulse height of signals in their cooled solid state detector, but rather crude spatial information. Our goal was to extract spectral information from the combined analysis of the Einstein and ROSAT images of Cas A and Tycho and to verify or refine the spectral map by checking its agreement with the BBSRT or ASCA spectra results for larger regions. In particular, we note that the Einstein and ROSAT telescopes have different spectral responses. The Einstein bandwidth includes the 2-4 keV region which is absent from ROSAT. Hence, by forming linear combinations of the Einstein and ROSAT images, we are able to resolve the contributions of the 0.5-2 keV band from the 2-4 keV band. The former contains lines of O and Fe while the latter is dominated by Si and S. We correct for the expansion that has taken place in the remnants during the ten-year interval between the Einstein and ROSAT measurements, but we must assume that no significant spectral changes have occurred during that time. The analysis of the Tycho SNR was completed and the results have been published. A copy of the paper is included. The analysis of Cas A has proved to be more complicated. It is continuing with support from another program. Part of the problem may be due to difficulties in the aspect information which is needed to precisely register the ROSAT and Einstein images.

Gorenstein, P.↗

Trace Element Geochemistry of Martian Iddingsite in the Lafayette Meteorite

The Lafayette meteorite contains abundant iddingsite, a fine-grained intergrowth of smectite clay, ferrihydrite, and ionic salt minerals. Both the meteorite and iddingsite formed on Mars. Samples of iddingsite, olivine, and augite pyroxene were extracted from Lafayette and analyzed for trace elements by instrumental neutron activation. Our results are comparable to independent analyses by electron and ion microbeam methods. Abundances of most elements in the iddingsite do not covary significantly. The iddingsite is extremely rich in Hg, which is probably terrestrial contamination. For the elements Si, Al, Fe, Mn, Ni, Co, and Zn, the composition of the iddingsite is close to a mixture of approximately 50% Lafayette olivine + approximately 40% Lafayette siliceous glass + approximately 1O% water. Concordant behavior among these elements is not compatible with element fractionations between smectite and water, but the hydrous nature and petrographic setting of the iddingsite clearly suggest an aqueous origin. These inferences are both consistent, however, with deposition of the iddingsite originally as a silicate gel, which then crystallized (neoformed) nearly isochemically. The iddingsite contains significantly more magnesium than implied by the model, which may suggest that the altering solutions were rich in Mg(2+).

Treiman, Allan H.↗

Lunar mining of oxygen using fluorine

An important aspect of lunar mining will be the extraction of volatiles, particularly oxygen, from lunar rocks. Thermodynamic data show that oxygen could readily be recovered by fluorination of abundant lunar anorthite, CaAl2Si2O8. Fluorine is the most reactive element, and the only reagent able to extract 100 percent of the oxygen from any mineral, yet it can safely be stored or reacted in nickel or iron containers. The general fluorination reaction, mineral + 2F2 = mixed fluorides = O2, has been used for more than 30 years at a laboratory scale by stable-isotope geochemists. For anorthite, metallic Al and Si may be recovered from the mixed fluorides by Na-reduction, and CaO via exchange with Na2O; the resulting NaF may be recycled into F2 and Na by electrolysis, using lanthanide-doped CaF2 as the inert anode.

Burt, Donald M.↗

Incineration as a Method for Resource Recovery from Inedible Biomass in a Controlled Ecological Life Support System

Resource recovery from waste streams in a space habitat is essential to minimize the resupply burden and achieve self-sufficiency. In a Controlled Ecological Life Support System (CELSS) human wastes and inedible biomass will represent significant sources of secondary raw materials necessary for support of crop plant production (carbon, water, and inorganic plant nutrients). Incineration, pyrolysis, and water extraction have been investigated as candidate processes for recovery of these important resources from inedible biomass in a CELSS. During incineration CO2 is produced by oxidation of the organic components and this product can be directly utilized by plants. Water is concomitantly produced, requiring only a phase change for recovery. Recovery of inorganics is more difficult, requiring solubilization of the incinerator ash. The process of incineration followed by water solubilization of ash resulted in loss of 35% of the inorganics originally present in the biomass. Losses were attributed to volatilization (8%) and non-water-soluble ash (27%). All of the ash remaining following incineration could be solubilized with acid, with losses resulting from volatilization only. The recovery for individual elements varied. Elemental retention in the ash ranged from 100% of that present in the biomass for Ca, P, Mg, Na, and Si to 10% for Zn. The greatest water solubility was observed for potassium with recovery of approximately 77% of that present in the straw. Potassium represented 80% of the inorganic constituents in the wheat straw, and because of slightly greater solubility made up 86% of the water-soluble ash. Following incineration of inedible biomass from wheat, 65% of the inorganics originally present in the straw were recovered by water solubilization and 92% recovered by acid solubilization. Recovery of resources is more complex for pyrolysis and water extraction. Recovery of carbon, a resource of greater mass than the inorganic component of biomass, is more difficult following pyrolysis and water extraction of biomass. In both cases, additional processors would be required to provide products equivalent to those resulting from incineration alone. The carbon, water, and organic resources of inedible biomass are effectively separated and output in usable forms through incineration.

Bubenheim, David L.↗

Petrology of four clasts from consortium breccia 73215

One felsite ('granite') and three ANT-suite anorthositic gabbro clasts extracted from breccia 73215 are described. The felsite clast has two components - fragments of crystalline felsite and veins and patches of felsic glass. The crystalline felsite, which consists largely of a vermicular intergrowth of quartz and Ba-K-feldspar, crystallized from a highly differentiated melt between 3.90 and 4.05 b.y. The felsic glass component consists of crystallized brown and colorless glasses and uncrystallized colorless glass which are all K and Si rich. The relation of glass features to past heating and the breccia-forming event is considered. In the three anorthositic gabbros, which have similar mineralogies and gradational textures, plagioclase is dominant, and olivine and orthopyroxene are the major mafic minerals. The petrologic data suggest that the gabbros formed as heated, partly melted, and/or recrystallized polymict breccias. It is possible that the approximately 4.25 b.y. age obtained for the three rocks is the date of the melting/recrystallization event.

James, O. B.↗

Nakhla: a Martian Meteorite with Indigenous Organic Carbonaceous Features

The Nakhla meteorite possesses discrete, well defined, structurally coherent morphologies of carbonaceous phases present within iddingsite alteration zones. Based upon both isotopic measurements and analysis of organic phases the presence of pre-terrestrial organics is now recognized. Within the microcrystalline layers of Nakhla s iddingsite, discrete clusters of salt crystals are present. These salts are predominantly halite (NaCl) with minor MgCl2 crystals. Some CaSO4, likely gypsum, appears to be partially intergrown with some of the halite. EDX mapping shows discrete C-rich features are interspersed among these crystals. A hollow semi-spherical bowl structure (~ 3 m ) has been identified and analyzed after using a focused ion beam (FIB) to cut a transverse TEM thin section of the feature and the underlying iddingsite. TEM/EDX analysis reveals that the feature is primarily carbonaceous containing C with lesser amounts of Si, S, Ca, Cl, F, Na, and minor Mn and Fe; additionally a small peak consistent with N, which has been previously seen in Nakhla carbonaceous matter, is also present. Selected area electron diffraction (SAED) shows that this C-rich material is amorphous (lacking any long-range crystallographic order) and is not graphite or carbonate. Micro-Raman spectra acquired from the same surface from which the FIB section was extracted demonstrate a typical kerogen-like D and G band structure with a weak absorption peak at 1350 and a stronger peak at 1600/cm. The C-rich feature is intimately associated with both the surrounding halite and underlying iddingsite matrix. Both iddingsite and salts are interpreted as having formed as evaporate assemblages from progressive evaporation of water bodies on Mars. This assemblage, sans the carbonaceous moieties, closely resembles iddingsite alteration features previously described which were interpreted as indigenous Martian assemblages. These distinctive macromolecular carbonaceous structures in Nakhla may represent one of the sources of the high molecular weight organic material previously identified in Nakhla. While we do not speculate on the origin of these unique carbonaceous structures, we note that the significance of such observations is that it may allow us to construct a C-cycle for Mars based on the C chemistry of the Martian meteorites with obvious implications for astrobiology and the prebiotic evolution of Mars. In any case, our observations strongly suggest that organic C exists as micrometersize, discrete structures on Mars.

McKay, D. S.↗

The chemical composition of the cores of the terrestrial planets and the moon

Using models of the quasi-chemical theory of solutions, the activity coefficients of silicon are calculated in the melts Fe-Si, Ni-Si, and Fe-Ni-Si. The calculated free energies of solution of liquid nickel and silicon in liquid iron in the interval 0 to 1400 kbar and 1500 to 4000 K, shows that Fe-Ni-Si alloy is stable under the conditions of the outer core of the earth and the cores of the terrestrial planets. The oxidation-reduction conditions are studied, and the fugacity of oxygen in the mantles of the planets and at the core-mantle boundary are calculated. The mechanism of reduction of silicon is analyzed over a broad interval of p and T. The interaction between the matter of the core and mantle is studied, resulting in the extraction of silicon from the mantle and its solution in the material of the core. It is concluded that silicon can enter into the composition of the outer core of the earth and Venus, but probably does not enter into the composition of the cores of Mercury, Mars, and the moon, if in fact the latter possesses one.

Kuskov, O. L.↗