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At least 19 records

Quantitative Mineralogical Analysis of Mars Analogues Using CHEMIN Data and Rietveld Refinement

Mineralogical analysis is a critical component of planetary surface exploration. Chemical data alone leave serious gaps in our understanding of the surfaces of planets where complex minerals may form in combination with H, S, and halogens. On such planets (e.g., Mars) a single chemical composition may represent a range of mineral assemblages. For example, Viking chemical analyses of excavated duricrust indicate that Mg and S are correlated and ~10% MgSO4 (anhydrous weight) is a likely cementing agent. Pathfinder chemical data support a similar abundance of MgSO4 in the most altered materials. However, there are many possible Mg-sulfates with widely varying hydration states (including dehydrated and 1-, 2-, 3-, 4-, 5-, 6-, and 7-hydrates). In addition, other sulfate minerals such as gypsum (CaSO4 .2H2O) and other salts containing Cl may also exist. X-ray diffraction (XRD) has the ability to decipher mixtures of these phases that would be difficult, if not impossible to unravel using only chemical or spectral data.

Bish, D. L.↗

Mineralogical and chemical characterization of iron-, manganese-, and copper-containing synthetic hydroxyapatites

The National Aeronautics and Space Administration's (NASA) Advanced Life Support (ALS) Program is evaluating the use of Fe-, Mn-, and Cu-containing synthetic hydroxyapatite (SHA) as a slow release fertilizer for crops that might be grown on the International Space Station or at Lunar and Martian outposts. Separate Fe-, Mn-, and Cu-containing SHA materials along with a transition-metal free SHA (pure-SHA) were synthesized using a precipitation method. Chemical and mineralogical analyses determined if and how Fe, Mn, and Cu were incorporated into the SHA structure. X-ray diffraction (XRD), Rietveld refinement, and transmission electron microscopy (TEM) confirmed that SHA materials with the apatite structure were produced. Chemical analyses indicated that the metal containing SHA materials were deficient in Ca relative to pure-SHA. The shift in the infrared PO4-mu 3 vibrations, smaller unit cell parameters, smaller particle size, and greater structural strain for Fe-, Mn-, and Cu-containing SHA compared with pure-SHA suggested that Fe, Mn, and Cu were incorporated into SHA structure. Rietveld analyses revealed that Fe, Mn, and Cu substituted into the Ca2 site of SHA. An Fe-rich phase was detected by TEM analyses and backscattered electron microscopy in the Fe-containing SHA material with the greatest Fe content. The substitution of metals into SHA suggests that metal-SHA materials are potential slow-release sources of micronutrients for plant uptake in addition to Ca and P.

NASA Center JSC↗

CHEMIN: A Mineralogical Dust Analyzer for the Odyssey Mission to Comet Kopff

The Odyssey spacecraft will be launched in June 2006 and will rendezvous with periodic Comet Kopff in September 2009. Odyssey will initially perform slow flybys of the active Kopff nucleus at distances between 500 and 100 km, and will then be placed in orbit around the nucleus at altitudes between 200 and 50 km. Odyssey's scientific payload of seven instruments includes CHEMIN, a mineralogical dust analyzer, which will make the first direct measurements of the crystal structure and elemental composition of cometary dust. CHEMIN will simultaneously perform X-ray Diffraction and X-ray Fluorescence (XRD/XRF) of individual 1-100 micron dust particles collected passively as the spacecraft is immersed in the comet's coma. The instrument has the geometry of a microfocus X-ray camera, with a postage stamp-sized energy-discriminating CCD in place of the film, and a miniature Cu target X-ray tube as the X-ray source. The CHEMIN flight instrument will weigh less than 2 kg., will have a total volume of about 1 liter, and will operate on 3 watts of power. Individual analyses will require 1-2 hours. XRD maxima from 5 to 65 degrees two-theta will be collected, encompassing definitive peaks for all known minerals. XRF data will be simultaneously collected for elements C through U. The instrument has sufficient resolution to allow Rietveld refinement of the diffraction data. Rock types as complex as basalt have been quantitatively analyzed using a CHEMIN laboratory prototype. Selected examples of diffraction experiments performed on more than 30 minerals and rock types by the CHEMIN laboratory prototype will be discussed.

Blake, David↗

Lunar and Planetary Science XXXV: The Future of Mars Surface Exploration

The session The Future of Mars Surface Exploration includes the following topics: 1) High Resolution Laser Scanning Techniques for Rock Abrasion and Texture Analyses on Mars and Earth; 2) Definitive Mineralogical Analysis of Mars Analog Rocks Using the CheMin XRD/XRF Instrument; 3) Quantitative Mineralogical Analysis of Mars Analogues Using CHEMIN Data and Rietveld Refinement; 4) In Situ Analytical Strategy for Mars Combining X-Ray and Optical Techniques; 5) In-Situ Dating on Mars: The Potential of OSL Dating; 6) Experiment of Dynamic Albedo of Neutrons (DAN): Searching for Water-rich Spots from the Rover on the Surface of Mars; and 7) Developing an Automated Science Analysis System for Mars Surface Exploration for MSL and Beyond.

Source record↗

Neutron Diffraction Study Oxygen Dissolution Alpha(sub 2)-Ti3Al

Rietveld refinements of neutron powder diffraction data on alpha(sub 2)-Ti3Al have been performed to determine the crystal structure as a function of interstitial oxygen (O) concentration for three alloys with a Ti/Al ratio of approximately equal to 2.34 and O concentrations of 0.25%, 3.99% and 7.71%. The structures of the allows are hexagonal in space group P6(sub 3)/mmc where Ti and Al atoms populate unique sites with excess Al at the Ti site and O atoms occupy octahedral interstitial sites surrounded by six Ti sites. The length of the c-axis was found to increase linearly as the O occupancy of the interstitial sites increased; this lattice lengthening effect was much less pronounced along the alpha axis. Correspondingly, the increases in the lengths of Ti-Al and Ti-Ti bonds with a major component of their direction parallel to the c-axis were roughly an order of magnitude greater than the increases in the lengths of Ti-al and Ti-Ti bonds more closely aligned with the alpha-axis. Densities calculated form the lattice parameters and occupancy factors fall in the range (4.118 plus or minus 0.004) grams per cubic centimeter to (4.194 plus or minus 0.004) grams per cubic centimeter, and exhibit a nearly linear increase with oxygen concentration. Measured densities of (4.113 plus or minus 0.001) grams per cubic centimeter, (4.146 plus or minus 0.009) grams per cubic centimeter, and (4.191 plus or minus 0.002) grams per cubic centimeter for these alloys agree with the results of the refinements.

Jones, Camille Y.↗

Detecting Nanophase Weathering Products with CheMin: Reference Intensity Ratios of Allophane, Aluminosilicate Gel, and Ferrihydrite

X-ray diffraction (XRD) data collected of the Rocknest samples by the CheMin instrument on Mars Science Laboratory suggest the presence of poorly crystalline or amorphous materials [1], such as nanophase weathering products or volcanic and impact glasses. The identification of the type(s) of X-ray amorphous material at Rocknest is important because it can elucidate past aqueous weathering processes. The presence of volcanic and impact glasses would indicate that little chemical weathering has occurred because glass is highly susceptible to aqueous alteration. The presence of nanophase weathering products, such as allophane, nanophase iron-oxides, and/or palagonite, would indicate incipient chemical weathering. Furthermore, the types of weathering products present could help constrain pH conditions and identify which primary phases altered to form the weathering products. Quantitative analysis of phases from CheMin data is achieved through Reference Intensity Ratios (RIRs) and Rietveld refinement. The RIR of a mineral (or mineraloid) that relates the scattering power of that mineral (typically the most intense diffraction line) to the scattering power of a separate mineral standard such as corundum [2]. RIRs can be calculated from XRD patterns measured in the laboratory by mixing a mineral with a standard in known abundances and comparing diffraction line intensities of the mineral to the standard. X-ray amorphous phases (e.g., nanophase weathering products) have broad scattering signatures rather than sharp diffraction lines. Thus, RIRs of X-ray amorphous materials are calculated by comparing the area under one of these broad scattering signals with the area under a diffraction line in the standard. Here, we measured XRD patterns of nanophase weathering products (allophane, aluminosilicate gel, and ferrihydrite) mixed with a mineral standard (beryl) in the CheMinIV laboratory instrument and calculated their RIRs to help constrain the abundances of these phases in the Rocknest samples.

Rampe, E. B.↗

Confidence Hills Mineralogy and Chemin Results from Base of Mt. Sharp, Pahrump Hills, Gale Crater, Mars

The Mars Science Laboratory (MSL) rover Curiosity recently completed its fourth drill sampling of sediments on Mars. The Confidence Hills (CH) sample was drilled from a rock located in the Pahrump Hills region at the base of Mt. Sharp in Gale Crater. The CheMin X-ray diffractometer completed five nights of analysis on the sample, more than previously executed for a drill sample, and the data have been analyzed using Rietveld refinement and full-pattern fitting to determine quantitative mineralogy. Confidence Hills mineralogy has several important characteristics: 1) abundant hematite and lesser magnetite; 2) a 10 angstrom phyllosilicate; 3) multiple feldspars including plagioclase and alkali feldspar; 4) mafic silicates including forsterite, orthopyroxene, and two types of clinopyroxene (Ca-rich and Ca-poor), consistent with a basaltic source; and 5) minor contributions from sulfur-bearing species including jarosite.

Cavanagh, P. D.↗

Thermochemistry of Rare Earth Silicates for Environmental Barrier Coatings

Rare earth silicates are promising candidates as environmental protective coatings (EBCs) for silica-forming ceramics and composites in combustion environments since they are predicted to have lower reactivity with the water vapor combustion products. The reactivity of rare earth silicates is assessed by the thermodynamic activity of the silica component which is best measured by Knudsen effusion mass spectrometry (KEMS). Here, we discuss a novel method based on a reducing agent to increase the partial pressure of SiO(g) which is then used to calculate thermodynamic activity of silica in Y2O3-SiO2 and Yb2O3-SiO2 systems. After the KEMS measurements, samples were probed by X-ray diffraction and their phase content was calculated from Rietveld refinement.

Rare Earth Silicates↗

The CheMin XRD on the Mars Science Laboratory Rover Curiosity: Construction, Operation, and Quantitative Mineralogical Results from the Surface of Mars

The Mars Science Laboratory mission was launched from Cape Canaveral, Florida on Nov. 26, 2011 and landed in Gale crater, Mars on Aug. 6, 2012. MSL's mission is to identify and characterize ancient "habitable" environments on Mars. MSL's precision landing system placed the Curiosity rover within 2 km of the center of its 20 X 6 km landing ellipse, next to Gale's central mound, a 5,000 meter high pile of laminated sediment which may contain 1 billion years of Mars history. Curiosity carries with it a full suite of analytical instruments, including the CheMin X-ray diffractometer, the first XRD flown in space. CheMin is essentially a transmission X-ray pinhole camera. A fine-focus Co source and collimator transmits a 50μm beam through a powdered sample held between X-ray transparent plastic windows. The sample holder is shaken by a piezoelectric actuator such that the powder flows like a liquid, each grain passing in random orientation through the beam over time. Forward-diffracted and fluoresced X-ray photons from the sample are detected by an X-ray sensitive Charge Coupled Device (CCD) operated in single photon counting mode. When operated in this way, both the x,y position and the energy of each photon are detected. The resulting energy-selected Co Kalpha Debye-Scherrer pattern is used to determine the identities and amounts of minerals present via Rietveld refinement, and a histogram of all X-ray events constitutes an X-ray fluorescence analysis of the sample.The key role that definitive mineralogy plays in understanding the Martian surface is a consequence of the fact that minerals are thermodynamic phases, having known and specific ranges of temperature, pressure and composition within which they are stable. More than simple compositional analysis, definitive mineralogical analysis can provide information about pressure/temperature conditions of formation, past climate, water activity and the like. Definitive mineralogical analyses are necessary to establish the origin or provenance of a sample. The search for evidence of extant or extinct life on Mars will initially be a search for evidence of present or past conditions supportive of life (e.g., evidence of water), not for life itself.Results of the first 1,000 sols (Mars days) will be discussed, including the discovery of the first habitable environment on Mars.

CheMin↗

Diagenesis in the Murray Formation, Gale Crater, Mars

The Mars Science Laboratory (MSL) Curiosity rover began investigating the rocks of Mt. Sharp in September 2014. The Murray formation is the lowermost unit, which is mostly comprised of finely laminated mudstones, suggesting these sediments were deposited in a lacustrine environment. It is important to characterize the geochemical and mineralogical trends throughout the Murray Fm to interpret the aqueous conditions of the ancient lake, the sources of the lake sediments, and post-depositional alteration processes. Four samples have been drilled from the Murray Fm so far: Confidence Hills, Mojave 2, and Telegraph Peak were collected from the Pahrump Hills member - the basal portion of the Murray Fm, and Buckskin was collected in the Marias Pass region (Fig. 1). The drill fines were delivered to the instruments inside the rover, including the CheMin instrument, a combination X-ray diffractometer and X-ray fluorescence spectrometer. Rietveld refinements and FULLPAT analyses of 1D CheMin XRD patterns were performed to determine quantitative abundances of minerals and amor-phous phases and the unit cell parameters of minerals present in abundances greater than 4-5 wt.%.

Rampe, E. B.↗

Mineralogy of Mudstone at Gale Crater, Mars: Evidence for Dynamic Lacustrine Environments

The Mars Science Laboratory Curiosity rover landed in Gale crater in August 2012 to assess the habitability of sedimentary deposits that show orbital evidence for diverse ancient aqueous environments. Gale crater contains a 5 km high mound of layered sedimentary rocks in its center, informally named Mount Sharp. The lowermost rocks of Mount Sharp contain minerals that are consistent with a dramatic climate change during Mars' early history. During the rover's traverse across the Gale crater plains to the base of Mount Sharp, Curiosity discovered sedimentary rocks consistent with a fluviolacustrine sequence. Curiosity studied ancient lacustrine deposits at Yellowknife Bay on the plains of Gale crater and continues to study ancient lacustrine deposits in the Murray formation, the lowermost unit of Mount Sharp. These investigations include drilling into the mudstone and delivering the sieved less than 150 micrometers fraction to the CheMin XRD/XRF instrument inside the rover. Rietveld refinement of XRD patterns measured by CheMin generates mineral abundances with a detection limit of 1-2 wt.% and refined unit-cell parameters of minerals present in abundances greater than approximately 5 wt.%. FULLPAT analyses of CheMin XRD patterns provide the abundance of X-ray amorphous materials and constrain the identity of these phases (e.g., opal-A vs. opal-CT). At the time of writing, CheMin has analyzed 14 samples, seven of which were drilled from lacustrine deposits. The mineralogy from CheMin, combined with in-situ geochemical measurements and sedimentological observations, suggest an evolution in the lake waters through time, including changes in pH and salinity and transitions between oxic and anoxic conditions. In addition to a geochemically dynamic lake environment, the igneous minerals discovered in the lake sediments indicate changes in source region through time, with input from mafic and silicic igneous sources. The Murray formation is predominantly comprised of lacustrine mudstone and is 150-200 m thick, suggesting long history of lake environments in Gale crater. Curiosity has traversed through the lowermost approximately 30 m of the Murray formation, and each additional sample provides clues about the climate on early Mars.

Rampe, E. B.↗

Mineralogy, Provenance, and Diagenesis of a Potassic Basaltic Sandstone on Mars: CheMin X-Ray Diffraction of the Windjana Sample (Kimberley Area, Gale Crater)

The Windjana drill sample, a sandstone of the Dillinger member (Kimberley formation, Gale Crater, Mars), was analyzed by CheMin X-ray diffraction (XRD) in the MSL Curiosity rover. From Rietveld refinements of its XRD pattern, Windjana contains the following: sanidine (21% weight, approximately Or(sub 95)); augite (20%); magnetite (12%); pigeonite; olivine; plagioclase; amorphous and smectitic material (approximately 25%); and percent levels of others including ilmenite, fluorapatite, and bassanite. From mass balance on the Alpha Proton X-ray Spectrometer (APXS) chemical analysis, the amorphous material is Fe rich with nearly no other cations-like ferrihydrite. The Windjana sample shows little alteration and was likely cemented by its magnetite and ferrihydrite. From ChemCam Laser-Induced Breakdown Spectrometer (LIBS) chemical analyses, Windjana is representative of the Dillinger and Mount Remarkable members of the Kimberley formation. LIBS data suggest that the Kimberley sediments include at least three chemical components. The most K-rich targets have 5.6% K2O, approximately 1.8 times that of Windjana, implying a sediment component with greater than 40% sanidine, e.g., a trachyte. A second component is rich in mafic minerals, with little feldspar (like a shergottite). A third component is richer in plagioclase and in Na2O, and is likely to be basaltic. The K-rich sediment component is consistent with APXS and ChemCam observations of K-rich rocks elsewhere in Gale Crater. The source of this sediment component was likely volcanic. The presence of sediment from many igneous sources, in concert with Curiosity's identifications of other igneous materials (e.g.,mugearite), implies that the northern rim of Gale Crater exposes a diverse igneous complex, at least as diverse as that found in similar-age terranes on Earth.

Treiman, Allan H.↗

Investigation of Magmatic Activities on Early Mars Using Igneous Mineral Chemistry in Gale Crater, Mars

One objective of rover missions is exploring the geological context of the surroundings. Over the years, igneous petrology and sedimentology have been disconnected, the first investigating magmatic processes and volcanic activities, and the second seeking environmental conditions in the past and assessing the habitability of the planet. Although different, one is related to the other: igneous rocks are altered and broken down, leading to the formation of sedimentary rocks, which can in turn be used to back out the nature of their magmatic source. The Curiosity rover that landed in the 3.7 Gyr old impact crater Gale is traveling through sedimentary rocks. About fifty float rocks have been observed, and several of them with ambiguous texture and composition have been classified as igneous or sedimentary depending on studies such as Jake_M. The composition of several unambiguous igneous rocks has been analyzed [4- 6] but their heterogeneity at a larger instrumental (measurement size < 2 cm) scale prevents the measurement of a bulk composition as performed on Earth. An original approach avoiding these two last issues is to consider igneous mineral chemistry analyzed within igneous and sedimentary rocks to assess magmatic processes that could have formed them. Most Curiosity data are used to explore ancient environmental conditions, and a significant number of compositional analyses are under-explored for constraining magmatic activities. We will present how we can make use of sedimentary data for investigating igneous processes in the vicinity of Gale crater. Geological Context: We focus on the first 750 martian days, corresponding to measurements in a coherent lacustrine sedimentary unit called Bradbury, because all sedimentary rocks were sourced from the same watershed and appear to have a consistent source with minimal alteration [2-3]. Igneous detrital minerals including feldspar and pyroxene, are observed in sedimentary rocks. Monte Carlo models showed that minimal cation loss is observed based on the composition of all Bradbury rocks, implying negligible weathering [3]. Although clay minerals are detected in few rocks [7], chemical compositions of rocks can be explained by a mixture of primary igneous minerals [3]. Variation of composition within Bradbury rocks can be explained by mineral sorting and one distinct source component. While a common magmatic source is suggested, Bradbury sediments likely come from several volcanic eruptions from a single magmatic chamber [9- 10]. The occurrence of alkali minerals like sanidine and K-rich rocks throughout Bradbury supports the presence of a potassic component, likely trachytic, while plagioclase and a mafic composition suggest a basaltic component [8-9]. Instruments: Mineral chemistry can be estimated by three instruments onboard Curiosity. The CheMin instrument enables detection of mineral assemblages using X-ray diffraction (XRD). Using Rietveld refinement, each mineral is identified according to their 1D XRD pattern [11]. Note that distinction between pyroxene minerals is challenging with the CheMin instrument due to overlapping peaks on XRD patterns and low angular resolution of the instrument [12]. Then, using least square regression and optimization algorithms based on unit-cell parameters, mineral chemistry has been estimated by [11]. Plagioclase composition has been estimated using the NaAlSi3O8- CaAl2Si2O8 system and alkali feldspar is based on the NaAlSi3O8-KAlSi3O8 system (stars in Fig.1). Two mudstone samples (John Klein and Cumberland) and one sandstone sample (Windjana) were analyzed by CheMin at Yellowknife Bay and Kimberley, respectively. Figure 1. Ternary diagrams of feldspars (top) and pyroxene (bottom) quadrilateral. Stars correspond to CheMin composition and the gray patches to ChemCam composition. The colored dots are the composition of feldspar and pyroxene that crystallized during fractional crystallization at FMQ+1 of a melt extracted at distinct melting degree during the adiabatic ascent of a primitive mantle composition, without any water (left panels) and with 0.5 wt.% of water (right panels) at distinct pressure. The ChemCam instrument enables the analysis of the chemical compositions of rocks at hundreds of micrometer scale (350-550 μm) using laser induced breakdown spectroscopy (LIBS), which may provide the composition of minerals when they are larger than the beam spot (>550 μm) [13]. Within >5000 LIBS points, we performed a typical stoichiometric filtering allowing us to distinguish 56 feldspar and 10 pyroxene mineral compositions (grey patches in Fig. 1). Finally, the Alpha Particle X-ray Spectrometer (APXS) analyzes the composition of rocks with a 1.6 cm diameter spot size. Monte Carlo mass balance modeling allowed [3] to decipher a feldspar range varying between An30 and An40 (Fig. 1). Discussion: Although there could be a more complex history and other ways to form the whole compositional range of igneous minerals analyzed within the Bradbury formation, we are presenting here simple magmatic pathways commonly occurring on Earth using the thermodynamical softwares pMELTS and rhyoliteMELTS [14]. The objective is to find reasonable igneous processes that produce minerals that parallel the compositions of feldspar and pyroxene analyzed by the Curiosity rover. As commonly observed for mid-ocean ridge basalts, the adiabatic ascent of a primitive mantle composition [15] partially melting at 2 GPa has been modeled, followed by the extraction of a liquid at distinct degrees of partial melting, which undergoes fractional crystallization at an oxygen fugacity +1 log unit above the fayalite-magnetite-quartz (FMQ) buffer within the crust (0.02-0.4 GPa) with H2O = 0- 0.5 wt. %. These latter conditions correspond to those recorded within igneous clasts from the Noachian martian breccia NWA 7034 and paired and within Gale igneous rocks (colored dots in Fig. 1) [16-17]. To check the reliability of these 2-step models, we also tested fractional crystallization at similar conditions (FMQ+1; P=0.02-0.4 GPa; H2O = 0-0.5 wt. %) of starting compositions corresponding to that of magmas with distinct melting degrees obtained from isobaric experiments at 2 GPa [18]. Mineral compositions obtained from both models are similar. As shown on Fig. 1, the whole range of observed feldspar compositions cannot be reproduced by fractionation of one magma only. Indeed, while alkali feldspar and Na-plagioclase likely crystallized from fractional crystallization of a low-degree melt (here <15%), plagioclase and pyroxene can only be formed by fractional crystallization of a higher degree melt (here >19%). The corresponding liquid descent lines are broadly in agreement with compositions estimated by ChemCam corresponding to float igneous rocks (Fig. 2) [4-6]. Figure 2. Silica versus alkali content. Lines show the liquid lines of descent from magmas with distinct degrees of melting. Gray patches represents the composition of Gale igneous rocks [4-6]. Trachytic to rhyolitic magmas crystallize alkali feldspar, and andesite to dacite magmas likely form plagioclase. Therefore, at least two starting magmas at distinct melting degrees, which could easily come from a single mantle source, are necessary to explain the whole compositional range of feldspar and pyroxene analyzed within Bradbury rocks. Conclusion: Because rocks from the Bradbury formation are likely originating from the same magmatic source with minimal weathering as supported by several studies using different approaches, igneous mineral chemistry analyzed by CheMin and ChemCam allows us to back out reasonable magmatic pathways that could have crystallized them. Fractional crystallization of at least two starting magmas originating from distinct melting degrees of a single mantle source can explain the whole range of feldspar and pyroxene composition. Both alkaline and sub-alkaline liquids can be produced, with compositions corresponding to those of the igneous rocks analyzed by ChemCam within the Bradbury formation, highlighting the complexity of Mars magmatism.

Payre, V.↗

Laboratory Investigation of the Effect of Venusian Weathering on Mineral Spectra

Introduction: The recent selection of two missions to Venus has renewed the importance of deter-mining weathering reactions between minerals and the Venusian atmosphere, and the spectral signatures of minerals before, during, and after these reactions. The rate at which weathering reactions progress also constrain show long unstable minerals will be present on the surface (e.g., [1]), and enables the use of mineralogy as a constraint on surface age(e.g., [2-3]).In order to gain an understanding of how mineral compositions and spectra change with weathering, we have begun conducting experiments in a 1 atm experimental setup at Wesleyan University. This setup exposes minerals to the temperature and most abundant gases of the Venus atmosphere (CO2, SO2, N2).We conducted initial experiments using biotite, calcite, and montmorillonite in order to test our methodology with minerals that may be relevant to recording the history of water on Venus. Methods: Experiments were conducted in Thermo Fisher Scientific Lindberg/Blue M Mini-Mite horizontal tube furnaces at Wesleyan University. Experiments used natural mineral chips and powders, and were conducted at 1 atmosphere and 460 °C under pre-mixed gases provided by Air Gas(Table 1). The furnaces are set up in a flow through configuration so that solid samples are exposed to a fixed gas composition, and quartz glass process tubes were used in all experiments (1/4” diameter for experiment V4, ½” diameter for all others). These conditions were maintained for the du-rations listed in Table 1, at which point the furnace was turned off with gas flowing until the sample was cool enough to extract under N2and be placed in a desiccator for storage. Run products were carbon coated and examined using a Hitachi SU5000 Field Emission Gun Scanning Electron Microscope (SEM) equipped with an EDAX Octane Pro EDS detector located at Wesley-an University. Visible-Near Infrared Spectroscopy (VNIR) analysis was performed on powdered samples under a nitrogen atmosphere using an ASD Fieldspec Proover the 350-2500 nm range. Powdered mineral samples were milled to a particle size of < 45μm and were spiked with an internal standard (Al2O3, corundum) to obtain quantitative mineralogy. Samples were analyzed using a Panalytical X’Pert pro X-ray Diffractometer (XRD), with an X’Celerator high speed detector and Co Kα radiation, with data collected at a step size of 0.02 ̊/minute step counting rate from 2 to 80 degrees 2θ at 45 mA/40kV in the X-ray Diffraction Laboratory located at NASA Johnson Space Center. Materials Data Inc (MDI) software suite, JadeTMv9 was used for Rietveld refinement to determine phase abundances and mineral identification by comparing XRD patterns to International Center for Diffraction Data (ICDD) database patterns. Table 1: Experimental matrix. Experiment Name Duration (Days)Gas Com-position (trace gas)MineralsV487SO2/N2(1.4%)Montmorillonite, biotiteV519SO2/N2(1.4%)CalciteV619CO2/SO2/N2(1.4% SO2, 2.1% N2)Montmorillonite, biotiteV828SO2/N2(1.4%)Biotite, calcite Results: Calcite. In both experiments, calcite was exposed to the SO2/N2gas mixture, and in both experimental run products, XRD analysis detected anhydrite, which is consistent with EDS measurements conducted in the SEM. The XRD analyses show greater amounts of anhydrite present after 28 days than 19, suggesting the calcite reaction progressed further given longer duration. Grain surface morphology as seen in the SEM also shows secondary mineral growth (Fig. 1). VNIR spectra show no change, as expected since anhydrite lacks spectral features in this wavelength range. Montmorillonite. Montmorillonite was exposed to two different gas mixtures, the SO2/N2mix and CO2/SO2/N2mix over different durations (87 and 19 days, respectively). VNIR analyses of both run products show a reduction in the 1441and1910 nm water features as well as a shift of the 1411 and 2011 nm features to shorter wavelengths that may indicate re-structuring in the crystal lattice and the production of amorphous phases [4]. XRD results are consistent with this, showing a shift of the 001 peak from 15Åto 10Åin both run products. The amount of X-ray amorphous material in the montmorillonite run products was greater than that present in the unreacted clay, being the greatest in the 87 day V4 experiment. No other secondary phases were detected in the run products, however sulfur was present in EDS analyses of powder samples.

A R Santos↗

Mineralogical, Elemental and Tomographic Reconnaissance Investigation for CLPS (“METRIC”)

METRIC comprises a suite of two instruments in a Lunar lander that perform X-ray diffraction (XRD) for mineral structure, X-ray fluorescence (XRF) for elemental composition, and X-ray Micro Computed Tomography (XCT) for 3D internal micromorphology. The instruments are accompanied by optical-near IR cameras to provide local geologic context. The Honeybee Robotics PlanetVac pneumatic sampling and transfer system [1],positioned on a lander footpad, will deliver sieved regolith to the X-ray instruments for analysis. The instrument suite is intended for delivery to the lunar surface on a Commercial Lunar Payload Services (CLPS) lander. The METRICXRD/F instrument draws on heritage from the Mars Science Laboratory CheMin instrument [2] and improves upon the design in multiple ways [3]. Like CheMin, Rietveld refinement and full-pattern fitting of METRIC XRD data can identify minerals at a detection limit of ~1 wt.%, quantify their abundances when present at >3 wt.%, and determine mineral composition (e.g., Fo#in olivine) from lattice parameters for minerals present at >5 wt.%[4,5]. An optimized XRF geometry provides for improved detection and quantification of major, minor and trace elements. The METRIC XCT instrument is a miniaturized X-ray Computed Tomography scanner[6]. Lunar regolith is delivered to a 3 mm diameter, 10 mm long graphite tube inside the instrument. The tube is rotated through 360°in 0.9deg.incrementsand a divergent point source X-ray beam is directed through the material. A Charge Coupled Device (CCD)records attenuation images whose brightness and contrast area function of average atomic number and density. Quantitative data, including particle and void sizes, 3D particle shape parameters, modal volumes and pore geometry can be derived from the resulting 3D reconstructions(voxel resolution: 30 μm). Crystal morphologies derived from METRIC XCT data complement the bulk mineralogy determined by the METRIC XRD/F and provide a measure of grain size distribution for the different phases. Taken together, the METRIC instrument suite determines crystal structure, elemental composition and morphology, three principal characteristics of geological materials that are highly useful in determining the origin and subsequent processing of lunar regolith.

Moon↗

Co(x)Ni(4-x)Sb(12-y)Sn(y) Ternary Skutterudites: Processing and Thermoelectric Properties

Skutterudites have proven to be a useful thermoelectric system as a result of their high figure of merit, favorable mechanical properties, and good thermal stability. Binary skutterudites have received the majority of interest in recent years, as a result of successful double and triple filling schemes. Ternary skutterudites, such as Ni4Sb7Sn5, also demonstrate good thermoelectric performance, with high power factor and low thermal conductivity. Ternary skutterudites, as contrasted to binary systems, provide more possibility for tuning electronic structure as substitutions can be studied on three elements. The Co(x)Ni(4-x)Sb(12-y)Sn(y) system has been investigated as both a p- and n-type thermoelectric material, stable up to 200 C. The system is processed through a combination of solidification, mechanical alloying, and hot pressing steps. Rietveld structure refinement has revealed an interesting occupancy of Sn on both the 24g Wyckoff position with Sb as well as the 2a position as a rattler. In addition to thermoelectric properties, detailed processing routes have been investigated on the system.

Seebeck effect↗

Crystal-Chemical Analysis of Soil at Rocknest, Gale Crater

The CheMin instrument on the Mars Science Laboratory rover Curiosity performed X-ray diffraction analysis on Martian soil [1] at Rocknest in Gale Crater. In particular, crystalline phases from scoop 5 were identified and analyzed with the Rietveld method [2]. Refined unit-cell parameters are reported in Table 1. Comparing these unit-cell parameters with those in the literature provides an estimate of the chemical composition of the crystalline phases. For instance, Fig. 1 shows the Mg-content of Fa-Fo olivine as a function of the b unit-cell parameter using literature data. Our refined b parameter is indicated by the black triangle.

Morrison, S. M.↗

X-Ray Diffraction Based Phase Identification in NiTiHf Shape Memory Alloys with Variable Hf Content

NiTiHf type shape memory alloys have been studied for use in high temperature actuator applications, the most studied of which is the NiTi-20Hf atomic % composition. In this study, six samples of NiTi-Hf including 20Hf, 30Hf, 35Hf, 40Hf, 45Hf, and 50Hf were evaluated by both 1D and 2D X-ray diffraction (XRD) to elucidate what phases and crystal structures were present at room temperature. Given small sample sizes and relatively large grains, multiple cross-sections were measured to increase the sampling statistics, and 2D XRD frames were collected to corroborate the 1D XRD data. Rietveld and structureless refinements were both performed, allowing for adjustments in orientation lattice constant, and structure factor. At room temperature, the primary martensitic phase in the NiTiHf alloys with 20 at% and lower Hf is a monoclinic B19’ phase (P1121/m space group). This phase was identifiable, even in small amounts, in the higher Hf samples. The primary phase in the 30 -50 at% Hf samples is an orthorhombic B33 (Cmcm space group) phase. This work supported thermal analyses indicating the phase transition paths from the two different room temperature martensitic phases to the B2 austenitic phase.

Laura Wilson↗