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At least 415 records · Page 23

Measuring the Chemical Potential of the Martian Regolith to Generate and Sustain Life

A critical component for identifying chemical biosignatures is the ability to assess in-situ the potential of an aqueous geochemical environment to generate and sustain life. On Mars or other solar bodies, in-situ chemical characterization could provide evidence as to whether the chemical composition of the regolith or evaporites in suspected ancient water bodies have been biologically influenced or possess the chemical parameters within which life may have existed, or may still exist. A variety of analytical techniques have been proposed for use in detecting and identify signatures of past or present life. These techniques fall into two groups; visual observation with instruments such as cameras or optical/atomic-force microscopes; or elemental chemical analysis with such instruments as X-ray fluorescence (XRF) and diffraction (XRD), a-proton backscatter (APX), y-ray, Mossbauer, Raman, IR, UV/VIS spectroscopies, gas chromatography (GC), or mass spectrometry (MS). Direct observation of an identifiable lifeform by the first set of instruments in a single sample is highly unlikely, especially for extinct organisms or on the surface. The later instruments can provide vital data as to the elemental mineralogy and geological history of the planet, but are highly inadequate for understanding the chemistry of the planet in terms of indigenous life or interactions with human explorers. Techniques such as XRD, XRF, and APX, provide elemental composition at high limits of detection. Some of this data can be extrapolated or interpolated to provide chemical parameters such as oxidation state or composition. Gas chromatography (GC) without standards and non-specific detectors, has little chance of identifying a mixture of unknown components. Combined with GC or by itself, mass spectrometry (MS) can provide identification of compounds, but in both cases the sample must be appropriately prepared for accurate and reliable analysis. Life as we know it, and probably identify it as such, requires an aqueous environment. Deciphering die chemical speciation of this aqueous environment is the key to recognizing therein the biosignatures of any extinct or present life forms. Identifying the soluble (ionic and nonionic) components by reacting a currently dormant environment can provide a "picture" of the thermodynamics and chemical components of a possibly bioactive environment. The only devices which can provide such information are electrochemical sensors based on the potentiometric ion selective electrodes (ISEs) and on dynamic techniques such as cyclic voltammetry (CV) and stripping voltammetry (SV). Such an array of devices can provide not only the chemical composition of a water-soluble Martian soil sample, but also several other vital chemical parameters such as pH, conductivity, redox potential, and dissolved gases. To address these issues we have been investigating the possible use of an electrochemically-based ion sensor array as a new integrated approach to quantitative analytical and chemometric electrochemical measurements. The sensor array will consist of specific and semispecific ion selective and amperometric transducers, which can simultaneously and continuously identify and semiquantitatively determine over 50 organic and inorganic analytes in water-based environments. Several individual sensors, based on the same principle, have been flight-tested and have been installed as part of the MECA instrumentation on the Mars 2001 Lander for in-situ analyses. However, the microfabrication, integration and multiplexing of such a large number of these sensors on a single substrate have not been previously attempted.

Kounaves, S. P.↗

X-Ray Fingerprinting Techniques for Recognizing A Hydrological Role in the Formation of Minerals on the Surface of Mars

Previous work has demonstrated the ability of a miniaturized XRD-XRF instrument to perform in-situ analyses without sample preparation or acquisition. Deployment of this instrument on a Martian rover will allow a large number of rapid qualitative analyses, which will maximize the diversity of samples studied and selected for possible return. As a first step in designing a decision tree for recognizing minerals in complex mixtures, d spacings were plotted against intensity for several mineral groups comprising rock and soil types inferred for the surface of Mars (weathered basalt, playa and hydrothermal deposits, clay-rich soils). In all groups, d spacings cluster in a range from about 1-4 angstroms, which can under certain circumstances obscure patterns for individual phases. However, within the silicate family, minerals containing either bound OH- or molecules of H20 (clays, micas, amphiboles, zeolites) are characterized by a shift of peaks to higher d spacings. Large d spacings (greater than about 7 angstroms) thus act as a first-order filter for distinguishing hydrous from anhydrous silicates. The ability to quickly verify the presence of silicates that have interacted with water has important implications for using mineral chemistry and structure to help decipher the hydrologic and atmospheric history of Mars. This represents a beginning for developing more sophisticated methods of pattern recognition. These will combine XRD and XRF analyses with optical data to rapidly7 discern environmentally diagnostic assemblages without the necessity of identifying every peak individual mineral phase.

Metzger, Ellen P.↗

Strategies and Technologies for In Situ Mineralogical Investigations on Mars

Surface landers on Mars (Viking and Pathfinder) have not revealed satisfying answers to the mineralogy and lithology of the planet's surface. In part, this results from their prime directives: Viking focused on exobiology, Pathfinder focused on technology demonstration. The analytical instruments on board the landers made admirable attempts to extract the mineralogy and geology of Mars, as did countless modeling efforts after the missions. Here we suggest a framework for elucidating martian, or any other planetary geology, through an approach that defines (a) type of information required, (b) explorational strategy harmonious with acquisition of these data, (c) interpretation approach to the data, (d) compatible mission architecture, (e) instrumentation for interrogating rocks and soil. (a) Data required: The composition of a planet is ordered at scales ranging from molecules to minerals to rocks, and from geological units to provinces to planetary-scale systems. The largest ordering that in situ compositional instruments can attempt to interrogate is rock type "aggregate" information. This is what the geologist attempts to identify first. From this, mineralogy can be either directly seen or inferred. From mineralogy can be determined elemental abundances and perhaps the state of the compounds as being crystalline or amorphous. Knowledge of rock type and mineralogy is critical for elucidating geologic process. Mars landers acquired extremely valuable elemental data, but attempted to move from elements to aggregates, but this can only be done by making many assumptions and sometimes giant leaps of faith. Data we believe essential are elements, minerals, degree of ordering of compounds, and the aggregate or rock type that these materials compose. (b) Explorational strategy: A lander should function as a surrogate geologist. Of the total landscape, a geologist sees much, but gives detailed attention to an infinitesimally small amount of what is seen. To acquire samples worth detailed scrutiny, as many samples as possible need examining at a cursory or reconnaissance level. A representative, statistically-meaningful sample number cannot be overemphasized. This maxim still applies to geological exploration of our own planet of which we have abundant knowledge. Analysis of many samples mandates low-power consumption per sample. (c) Data interpretation: No single instrument can analyze the full spectrum of the x-axis. An instrument is optimized for detecting certain material characteristics and must therefore affix itself to some point on the x-axis. Any conclusions drawn about data to the left or right of the instrument's position on this axis must necessarily be derived by inference. Hence, it seems logical to include on a mission, instruments that are not closely spaced in their x-axis-position, and if only two analytical methods are used, as shown, they should start at opposite ends of the axis and work towards the center. As examples, we depict a high-resolution camera to evaluate rock type ("aggregate" state) and mineralogy, and an x-ray diffractometer-fluorescence spectrometer (XRD-XRF) to determine elements, minerals, and the degree of order of materials. (d) Mission architecture: No instrument or suite of instruments can be relied upon to always give truly unequivocal analyses. The suite of instruments should therefore permit conclusions of one instrument to be checked against those of another through closed analytical loops. These "loops" can be structured by a combination of orbital imagery, descent imagery, broad-band site viewing/analysis, and data that cover both x and y axes. For example, the detection of a basaltic-looking rock with a microscope should be checked against the elements detected, the appearance of the rock as a lava flow from descent imagery, and so forth. (e) Instrumentation: To satisfy the above criteria, it is necessary to: (i) See the rock or soil with high resolution + magnification, (ii) Examine many samples, (iii) Consume little power per analysis, (iv) Determine elemental species, (v) Determine mineralogy directly (not inferentially) and the degree of ordering of compounds, (vi) Start analyzing from both ends of the x-axis. Every geologist wants to see the hand sample first, and apply a hand lens to its surface. This has not been the starting point for missions to Mars. Thus, our technology satisfies all these criteria . This XRD-XRF-Optical instrument currently being developed, analyses rock or soil surfaces without the need for sample acquisition or preparation; this satisfies the power criterion, and enables many analyses. The device acquires direct mineralogy and determines elemental species. The embedded endoscopic camera satisfies the critical criterion of close inspection of samples; the fiber optic cable can also be used for IR, LTV, or laser sample analysis. Additional information is contained in the original (Figures).

Marshall, J. R.↗

Physical and Chemical Study of Minerals and Rocks Containing Low-Z Compounds of Interest to Astrobiology and Origin of Life

Understanding the origins of Life requires a good understanding of the physics and chemistry of biogenic low-z elements H, C, N, O, P, S in terrestrial environments, on Mars, on extraterrestrial bodies such as meteorite parent bodies and comets, and in interstellar space. In this Proposal five Tasks form a coherent program aimed at elucidating various aspects of low-z element geo- and cosmochemistry with special reference to the origin of Life on Earth and to the search for life on Mars, extant or extinct. (i) Formation of organic molecules, in particular oxygenated H-C-0 molecules or precursors thereof of the composition H(x)C(y)O(z)(n-), inside the hard matrix of structurally dense magmatic minerals; (ii) Formation of organic molecules inside the soft matrix of amorphous and crystalline water ice; (iii) Preservation of organic molecules in cherts and other siliceous rocks formed in hot spring or submarine hydrothermal vent environments; (iv) The nature of the elusive Martian soil oxidant; and (v) Prototype development of an XRD instrument, using a new patented XRD camera concept that utilizes a Charge Coupled Device (CCD) as a camera and as a energy-dispersive analyzer.

Source record↗

Spectroscopic and Geochemical Analyses of Ferrihydrite from Hydrothermal Springs in Iceland and Applications to Mars

Ferrihydrite samples were collected from a thermal spring and a cold stream in the Landmannalaugar region of Iceland. Chemical and spectroscopic analyses have been performed on the air-dried and fine-grained fractions of these samples. The ferrihydrite from the cold stream is a pure sample, containing small amounts of Ca, P and Si, which do not form minerals detectable with X-ray diffraction (XRD) or reflectance and transmittance spectroscopy. The ferrihydrite from the thermal pool is a less pure sample, containing larger amounts of amorphous Si and P. The XRD and spectral features for this sample are also consistent with a less crystalline structure. Some of the Si is incorporated in the structure of the ferrihydrite. The Ca, P and possibly some of the Si may be biogenic. The spectral character of these Icelandic ferrihydrites is compared with those of synthetic ferrihydrites and other iron oxide/oxyhydroxide minerals. Ferrihydrite is characterized by a broad Fe3+ excitation band near 0.92 microns (approx. 10900/cm) and a strong Fe-O absorption feature near 475/cm (approx. 21 microns) in transmittance spectra. Multiple bands due to H2O and OH are also present for ferrihydrite. Natural ferrihydrites frequently exhibit a band near 950-1050/cm (approx. 10 microns) that is typically not observed for synthetic ferrihydrites and may be due to some Si in the structure. An additional pair of spectral bands near 1400 and 1500/cm (approx. 7 microns) are characteristic of pure ferrihydrites from natural and synthetic sources. Hydrothermal springs may have been present at one time on Mars in association with volcanic activity. Ferrihydrite formation in such an environment may have contributed to the ferric oxide-rich surface material on Mars.

Bishop, Janice↗

Band-gap Engineering in Sputter Deposited Amorphous/Microcrystalline Sc(x)Ga(1-x)N

Reactive sputtering was used to grow thin films of Sc(x)Ga(1-x)N with scandium concentrations of 20%-70% on quartz substrates at temperatures of 300-675 K. X-ray diffraction (XRD) of the films showed either weak or no structure, suggesting the films are amorphous or microcrystalline. Optical absorption spectra were taken of each sample and the optical band gap was determined. The band gap varied linearly with increasing Ga concentration between 2.0 and 3.5 eV. Ellipsometry was used to confirm the band gap measurements and provide optical constants in the range 250-1200 nm. ScN and GaN have different crystal structures (rocksalt and wurzite, respectively), and thus may form a heterogeneous mixture as opposed to an alloy. Since the XRD data were inconclusive, bilayers of ScN/GaN were grown and optical absorption spectra taken. A fundamental difference in the spectra between the bilayer films and alloy films was seen, suggesting the films are alloys, not heterogeneous mixtures.

Little, Mark E.↗

Use of an Ultrasonic/Sonic Driller/Corer to Obtain Sample Powder for CHEMIN, a Combined XRD/XRF Instrument

A miniature CHEMIN XRD/XRF (X-Ray Diffraction/X-Ray Fluourescence) instrument is currently being developed for definitive mineralogic analysis of soils and rocks on Mars. One of the technical issues that must be addressed in order to enable XRD analysis on an extraterrestrial body is how best to obtain a representative sample powder for analysis. For XRD powder diffraction analyses, it is beneficial to have a fine-grained sample to reduce preferred orientation effects and to provide a statistically significant number of crystallites to the X-ray beam. Although a 2-dimensional detector as used in the CHEMIN instrument will produce good results with poorly prepared powders, the quality of the data will improve if the sample is fine-grained and randomly oriented. An Ultrasonic/Sonic Driller/Corer (USDC) currently being developed at JPL is an effective mechanism of sampling rock to produce cores and powdered cuttings. It requires low axial load (< 5N) and thus offers significant advantages for operation from lightweight platforms and in low gravity environments. The USDC is lightweight (<0.5kg), and can be driven at low power (<5W) using duty cycling. It consists of an actuator with a piezoelectric stack, ultrasonic horn, free-mass, and drill bit. The stack is driven with a 20 kHz AC voltage at resonance. The strain generated by the piezoelectric is amplified by the horn by a factor of up to 10 times the displacement amplitude. The tip impacts the free-mass and drives it into the drill bit in a hammering action. The free-mass rebounds to interact with the horn tip leading to a cyclic rebound at frequencies in the range of 60-1000 Hz. It does not require lubricants, drilling fluid or bit sharpening and it has the potential to operate at high and low temperatures using a suitable choice of piezoelectric material. To assess whether the powder from an ultrasonic drill would be adequate for analyses by an XRD/XRF spectrometer such as CHEMIN, powders obtained from the JPL ultrasonic drill were analyzed and the results were compared to carefully prepared powders obtained using a laboratory bench scale Retsch mill.

Chipera, S. J.↗

Laboratory Reflectance Spectra of 160 Minerals, 0.4 to 2.5 Micrometers

This reports provides reflectance spectra of 160 minerals in both digital and printed form. In order to demonstrate the effect of particle size on reflectance, the spectral data for 135 of the minerals are presented at three different grain sizes. These are 125-500 microns, 45-125 microns and less than 45 microns. Ancillary information is provided with each mineral spectrum, which includes the mineral name, minerology, supplier, sampling locality and our designated sample number. The purity of every mineral sample was evaluated by X-ray diffraction (XRD). The composition of certain minerals known to deviate strongly from idealized end-member compositions was determined by electron microprobe analysis. The compositional information obtained by microbe analysis and accessory minerals identified by XRD are noted with the ancillary information. In addition, the spectrum acquired from the coarsest grain size available for each sample was processed with a feature-finding algorithm to quantify the characteristics of the spectral absorption features. All the reflectance spectra presented here are provided in digital form on IBM-compatible 3.5" diskettes. Also included on diskette is a program for displaying the spectral data and searching for spectral features that runs on an IBM-compatible PC with standard VCA graphics.

reflectance spectra↗

Drilling on the Moon and Mars: Developing the Science Approach for Subsurface Exploration with Human Crews

DOMEX (Drilling on the Moon and Mars in Human Exploration) is using analog missions to develop the approach for using human crews to perform science activities on the Moon and Mars involving exploration and sampling of the subsurface. Subsurface science is an important activity that may be uniquely enabled by human crews. DOMEX provides an opportunity to plan and execute planetary mission science activities without the expense and overhead of a planetary mission. Objectives: The objective of this first in a series of DOMEX missions were to 1) explore the regional area to understand the geologic context and determine stratigraphy and geologic history of various geologic units in the area. 2) Explore for and characterize sites for deploying a deep (10 m depth) drilling system in a subsequent field season. 3) Perform GPR on candidate drill sites. 4) Select sites that represent different geological units deposited in different epochs and collect soil cores using sterile procedures for mineralogical, organic and biological analysis. 5) Operate the MUM in 3 different sites representing different geological units and soil characteristics. 6) Collect rock and soil samples of sites visited and analyze them at the habitat. Results: At mission start the crew performed a regional survey to identify major geologic units that were correlated to recognized stratigraphy and regional geologic maps. Several candidate drill sites were identified. During the rest of the mission, successful GPR surveys were conducted in four locations. Soil cores were collected in 5 locations representing soils from 4 different geologic units, to depths up to 1m. Soil cores from two locations were analyzed with PCR in the laboratory. The remainder were reserved for subsequent analysis. XRD analysis was performed in the habitat and in the field on 39 samples, to assist with sample characterization, conservation, and archiving. MUM was deployed at 3 field locations and 1 test location (outside the habitat) where it operated autonomously for 2-4 hours at each site. Depths achieved ranged from 15 to 70 cm depending on the soil compressive strength and the presence and depth of subsurface indurated layers. Subsurface samples weighing 0.5 to 1 g were collected at the deepest depth encountered at each of the sites using the MUM automated sample collection system, and subsequently analyzed with XRD. Downhole inspection of holes produced by MUM with the Raman spectrometer was acquired on two of the holes and spectral features associated with selenite were identified in specific soil layers. Previously unreported fossilized remains of vertebrate fauna from the Jurassic era were discovered during our mission. Analysis of mineral biomarkers associated with this discovery are underway.

Stoker, C. R.↗

Preliminary Geological Findings on the BP-1 Simulant

A waste material from an aggregate producing quarry has been used to make an inexpensive lunar simulant called BP-1. The feedstock is the Black Point lava flow in northern Arizona. Although this is part of the San Francisco volcanic field, which is also the source of the JSC-1 series feedstock, BP-1 and JSC-1 are distinct. Chemically, the Black Point flow is an amygdaloidal nepheline-bearing basalt. The amygdules are filled with secondary minerals containing opaline silica, calcium carbonate, and ferric iron minerals. X-ray diffraction (XRD) detected approximately 3% quartz, which is in line with tests done by the Kennedy Space Center Industrial Hygiene Office. Users of this material should use appropriate protective equipment. XRD also showed the presence of significant halite and some bassanite. Both are interpreted to be evaporative residues due to recycling of wash water at the quarry. The size distribution of BP-1 may be superior to some other simulants for some applications.

Stoeser, D. B.↗

Three Dimensional Structures of Particles Recovered from the Asteroid Itokawa by the Hayabusa Mission and a Role of X-Ray Microtomography in the Preliminary Examination

Particles of regolith on S-type Asteroid 25143 Itokawa were successfully recovered by the Hayabusa mission of JAXA (Japan Aerospace Exploration Agency). Near-infrared spectral study of Itokawa s surface indicates that these particles are materials similar to LL5 or LL6 chondrites. High-resolution images of Itokawa's surface suggest that they may be breccias and some impact products. At least more than 1500 particles were identified as Itokawa origin at curation facility of JAXA. Preliminary analysis with SEM/EDX at the curation facility shows that they are roughly similar to LL chondrites. Although most of them are less than 10 micron in size, some larger particles of about 100 micron or larger were also identified. A part of the sample (probably several tens particles) will be selected by Hayabusa sample curation team, and sequential examination will start from January 2011 by Hayabusa Asteroidal Sample Preliminary Examination Team (HASPET). In mainstream of the analytical flow, each particle will be examined by microtomography, XRD and XRF first as nondestructive analyses, and then the particle will be cut by an ultra-microtome and examined by TEM, SEM, EPMA, SIMS, PEEM/XANES, and TOF-SIMS sequentially. Three-dimensional structures of Itokawa particles will be obtained by microtomography sub-team of HASPET. The results together with XRD and XRF will be used for design of later destructive analyses, such as determination of cutting direction and depth, to obtain as much information as possible from small particles. Scientific results and a role of the microtomography in the preliminary examination will be presented.

Tsuchiyama, A.↗

Detection Limit of Smectite by Chemin IV Laboratory Instrument: Preliminary Implications for Chemin on the Mars Science Laboratory Mission

The CheMin instrument on the Mars Science Laboratory (MSL) is an miniature X-ray diffraction (XRD) and X-ray fluorescence (XRF) instrument capable of detecting the mineralogical and elemental compositions of rocks, outcrops and soils on the surface of Mars. CheMin uses a microfocus-source Co X-ray tube, a transmission sample cell, and an energy-discriminating X-ray sensitive CCD to produce simultaneous 2-D XRD patterns and energy-dispersive X-ray histograms from powdered samples. CRISM and OMEGA have identified the presence of phyllosilicates at several locations on Mars including the four candidate MSL landing sites. The objective of this study was to conduct preliminary studies to determine the CheMin detection limit of smectite in a smectite/olivine mixed mineral system.

Archilles, Cherie↗

Oxide Scales Formed on NiTi and NiPtTi Shape Memory Alloys

Ni-49Ti and Ni-30Pt-50Ti (at.%) shape memory alloys were oxidized isothermally in air over the temperature range of 500 to 900 C. The microstructure, composition, and phase content of the scales were studied by SEM, EDS, XRD, and metallography. Extensive plan view SEM/EDS identified various features of intact or spalled scale surfaces. The outer surface of the scale was a relatively pure TiO2 rutile structure, typified by a distinct highly striated and faceted crystal morphology. Crystal size increased significantly with temperature. Spalled regions exhibited some porosity and less distinct features. More detailed information was obtained by correlation of SEM/EDS studies of 700 C/100 hr cross-sections with XRD analyses of serial or taper-polishing of plan surfaces. Overall, multiple layers exhibited graded mixtures of NiO, TiO2, NiTiO3, Ni(Ti) or Pt(Ni,Ti) metal dispersoids, Ni3Ti or Pt3Ti depletion zones, and substrate, in that order. The NiTi alloy contained a 3 at.% Fe impurity that appeared in embedded localized Fe-Ti-rich oxides, while the NiPtTi alloy contained a 2 v/o dispersion of TiC that appeared in lower layers. The oxidation kinetics of both alloys (in a previous report) indicated parabolic growth and an activation energy (250 kJ/mole) near those reported in other Ti and NiTi studies. This is generally consistent with TiO2 existing as the primary scale constituent, as described here.

Smialek, James L.↗

Effects of Kapton Sample Cell Windows on the Detection Limit of Smectite: Implications for CheMin on the Mars Science Laboratory Mission

The CheMin instrument on the Mars Science Laboratory (MSL) rover Curiosity is an X-ray diffraction (XRD) and X-ray fluorescence (XRF) instrument capable of providing the mineralogical and chemical compositions of rocks and soils on the surface of Mars. CheMin uses a microfocus X-ray tube with a Co target, transmission geometry, and an energy-discriminating X-ray sensitive CCD to produce simultaneous 2-D XRD patterns and energy-dispersive X-ray histograms from powdered samples. CheMin has two different window materials used for sample cells -- Mylar and Kapton. Instrument details are provided elsewhere. Fe/Mg-smectite (e.g., nontronite) has been identified in Gale Crater, the MSL future landing site, by CRISM spectra. While large quantities of phyllosilicate minerals will be easily detected by CheMin, it is important to establish detection limits of such phases to understand capabilities and limitations of the instrument. A previous study indicated that the (001) peak of smectite at 15 Ang was detectable in a mixture of 1 wt.% smectite with olivine when Mylar is the window material for the sample cell. Complications arise when Kapton is the window material because Kapton itself also has a diffraction peak near 15 Ang (6.8 deg 2 Theta). This study presents results of mineral mixtures of smectite and olivine to determine smectite detection limits for Kapton sample cells. Because the intensity and position of the smectite (001) peak depends on the hydration state, we also analyzed mixtures with "hydrated" and "dehydrated"h smectite to examine the effects of hydration state on detection limits.

Achilles, C. N.↗

Visible and Near-IR Reflectance Spectra of Smectite Acquired Under Dry Conditions for Interpretation of Martian Surface Mineralogy

Visible and near-IR (VNIR) spectra from the MEx OMEGA and the MRO CRISM hyper-spectral imaging instruments have spectral features associated with the H2O molecule and M OH functional groups (M = Mg, Fe, Al, and Si). Mineralogical assignments of martian spectral features are made on the basis of laboratory VNIR spectra, which were often acquired under ambient (humid) conditions. Smectites like nontronite, saponite, and montmorillionite have interlayer H2O that is exchangeable with their environment, and we have acquired smectite reflectance spectra under dry environmental conditions for interpretation of martian surface mineralogy. We also obtained chemical, Moessbauer (MB), powder X-ray diffraction (XRD), and thermogravimetric (TG) data to understand variations in spectral properties. VNIR spectra were recorded in humid lab air at 25-35C, in a dynamic dry N2 atmosphere (50-150 ppmv H2O) after exposing the smectite samples (5 nontronites, 3 montmorillionites, and 1 saponite) to that atmosphere for up to approximately l000 hr each at 25-35C, approximately 105C, and approximately 215C, and after re-exposure to humid lab air. Heating at 105C and 215C for approximately 1000 hr is taken as a surrogate for geologic time scales at lower temperatures. Upon exposure to dry N2, the position and intensity of spectral features associated with M-OH were relatively insensitive to the dry environment, and the spectral features associated with H2O (e.g., approximately 1.90 micrometers) decreased in intensity and are sometimes not detectable by the end of the 215C heating step. The position and intensity of H2O spectral features recovered upon re-exposure to lab air. XRD data show interlayer collapse for the nontronites and Namontmorillionites, with the interlayer remaining collapsed for the latter after re-exposure to lab air. The interlayer did not collapse for the saponite and Ca-montmorillionite. TG data show that the concentration of H2O derived from structural OH was invariant to the dry N2 treatment for saponite and the montmorillionites, but the nontronites had additional structural OH after treatment. Upon exposure to dry N2, the VNIR spectra also acquired a red slope with decreasing albedo between approximately 0.4 and approximately 2.0 micrometers. The magnitude of the effects covaries with exposure time to dry N2 and heating temperature. Upon re-exposure to lab air, the slope and albedo do not completely recover to pre-exposure values. MB data show that these effects do not result from partial reduction of ferric to ferrous iron, and TG data show they do not result from loss of structural OH. Possible explanations include formation of small clusters of (superparamagnetic) ferric oxide and reduced smectite crystallinity. The difference in spectral properties between spectra acquired in humid lab air and under dry conditions are consequential for interpretation of CRISM and OMEGA spectra. For example, nontronite by itself and not nontronite plus ferrihydrite can account for the red spectral slope in martian spectra where nontronite is indicated by the Fe-OH spectral features.

Morris, Richard V.↗

Transmission Electron Microscopy (TEM) Sample Preparation of Si(1-x)Gex in c-Plane Sapphire Substrate

The National Aeronautics and Space Administration-invented X-ray diffraction (XRD) methods, including the total defect density measurement method and the spatial wafer mapping method, have confirmed super hetero epitaxy growth for rhombohedral single crystalline silicon germanium (Si1-xGex) on a c-plane sapphire substrate. However, the XRD method cannot observe the surface morphology or roughness because of the method s limited resolution. Therefore the authors used transmission electron microscopy (TEM) with samples prepared in two ways, the focused ion beam (FIB) method and the tripod method to study the structure between Si1-xGex and sapphire substrate and Si1?xGex itself. The sample preparation for TEM should be as fast as possible so that the sample should contain few or no artifacts induced by the preparation. The standard sample preparation method of mechanical polishing often requires a relatively long ion milling time (several hours), which increases the probability of inducing defects into the sample. The TEM sampling of the Si1-xGex on sapphire is also difficult because of the sapphire s high hardness and mechanical instability. The FIB method and the tripod method eliminate both problems when performing a cross-section TEM sampling of Si1-xGex on c-plane sapphire, which shows the surface morphology, the interface between film and substrate, and the crystal structure of the film. This paper explains the FIB sampling method and the tripod sampling method, and why sampling Si1-xGex, on a sapphire substrate with TEM, is necessary.

Kim, Hyun Jung↗

Data from the Mars Science Laboratory CheMin XRD/XRF Instrument

The CheMin instrument on the Mars Science Laboratory (MSL) rover Curiosity uses a Co tube source and a CCD detector to acquire mineralogy from diffracted primary X-rays and chemical information from fluoresced X-rays. CheMin has been operating at the MSL Gale Crater field site since August 5, 2012 and has provided the first X-ray diffraction (XRD) analyses in situ on a body beyond Earth. Data from the first sample collected, the Rocknest eolian soil, identify a basaltic mineral suite, predominantly plagioclase (approx.An50), forsteritic olivine (approx.Fo58), augite and pigeonite, consistent with expectation that detrital grains on Mars would reflect widespread basaltic sources. Minor phases (each <2 wt% of the crystalline component) include sanidine, magnetite, quartz, anhydrite, hematite and ilmenite. Significantly, about a third of the sample is amorphous or poorly ordered in XRD. This amorphous component is attested to by a broad rise in background centered at approx.27deg 2(theta) (Co K(alpha)) and may include volcanic glass, impact glass, and poorly crystalline phases including iron oxyhydroxides; a rise at lower 2(theta) may indicate allophane or hisingerite. Constraints from phase chemistry of the crystalline components, compared with a Rocknest bulk composition from the APXS instrument on Curiosity, indicate that in sum the amorphous or poorly crystalline components are relatively Si, Al, Mg-poor and enriched in Ti, Cr, Fe, K, P, S, and Cl. All of the identified crystalline phases are volatile-free; H2O, SO2 and CO2 volatile releases from a split of this sample analyzed by the SAM instrument on Curiosity are associated with the amorphous or poorly ordered materials. The Rocknest eolian soil may be a mixture of local detritus, mostly crystalline, with a regional or global set of dominantly amorphous or poorly ordered components. The Rocknest sample was targeted by MSL for "first time analysis" to demonstrate that a loose deposit could be scooped, sieved to <150 microns, and delivered to instruments in the body of the rover. A drilled sample of sediment in outcrop is anticipated. At the time of writing this abstract, promising outcrops are in range and this talk will provide an update on data collected with the CheMin instrument.

Vaniman, David↗

Alteration of Basaltic Glass to Mg/Fe-Smectite under Acidic Conditions: A Potential Smectite Formation Mechanism on Mars

Phyllosilicates of the smectite group including Mg- and Fe-saponite and Fe(III)-rich nontronite have been identified on Mars. Smectites are believed to be formed under neutral to alkaline conditions that prevailed on early Mars. This hypothesis is supported by the observation of smectite and carbonate deposits in Noachian terrain on Mars. However, smectite may have formed under mildly acidic conditions. Abundant smectite formations have been detected as layered deposits hundreds of meters thick in intracrater depositional fans and plains sediments, while no large deposits of carbonates are found. Development of mildly acidic conditions at early Mars might allow formation of smectite but inhibit widespread carbonate precipitation. Little is known regarding the mechanisms of smectite formation from basaltic glass under acidic conditions. The objective of this study was to test a hypothesis that Mars-analogue basaltic glass alters to smectite minerals under acidic conditions (pH 4). The effects of Mg and Fe concentrations and temperature on smectite formation from basaltic glass were evaluated. Phyllosilicate synthesis was performed in batch reactors (Parr acid digestion vessel) under reducing hydrothermal conditions at 200 C and 100 C. Synthetic basaltic glass with a composition similar to that of the Gusev crater rock Adirondack (Ground surface APXS measurement) was used in these experiments. Basaltic glass was prepared by melting and quenching procedures. X-ray diffraction (XRD) analysis indicated that the synthesized glass was composed of olivine, magnetite and X-ray amorphous phase. Samples were prepared by mixing 250 mg Adirondack with 0.1 M acetic acid (final pH 4). In order to study influence of Mg concentration on smectite formation, experiments were performed with addition of 0, 1 and 10 mM MgCl2. After 1, 7 and 14 day incubations the solution composition was analyzed by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and the altered glass and formed phyllosilicates were examined by XRD analysis. Mineralogical changes were significant in Adirondack incubated with 10 mM MgCl2 at pH 4 and heated at 200 C. X-ray diffraction analysis revealed formation of phyllosilicate during 14 day incubation (Figure 1). Smectite was confirmed as the phyllosilicate after treatments with glycerol and KCl and heating to 550 C. The position of 02l (4.60 A) and 060 (1.54 A) diffraction bands were indicative of trioctahedral smectite such as saponite. Analysis of solution composition demonstrated that aqueous concentration of Mg decreased from 10 mM to approx.4 mM after 7 day incubation likely due to saponite formation. Smectite also formed in Adirondack incubated with 0 mM MgCl2 at pH 4 and heated at 200 C. However, diffraction peak positions of 02l (4.52 A) and 060 (1.51 A) suggested formation of dioctahedral nontronite. The 100degC Mg and Fe(II) treated basaltic glass experiments are ongoing and results will be presented.

Peretyazhko, Tanya↗