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Investigations Using Laboratory Testbeds to Interpret Flight Instrument Datasets from Mars Robotic Missions

The Astromaterials Research and Exploration Science Directorate at the NASA Johnson Space Center (JSC) has laboratory instrumentation that mimic the capabilities of corresponding flight instruments to enable interpretation of datasets returned from Mars robotic missions. The lab instruments have been and continue to be applied to datasets for the Moessbauer Spectrometer (MB) on the Mars Exploration Rovers (MER), the Thermal & Evolved Gas Analyzer (TEGA) on the Mars Phoenix Scout, the CRISM instrument on the Mars Reconnaissance Orbiter Missions and will be applied to datasets for the Sample Analysis at Mars (SAM), Chemistry and Mineralogy (CheMin) and Chemistry & Camera (ChemCam) instruments onboard the Mars Science Laboratory (MSL). The laboratory instruments can analyze analog samples at costs that are substantially lower than engineering models of flight instruments, but their success to enable interpretation of flight data depends on how closely their capabilities mimic those of the flight instrument. The JSC lab MB instruments are equivalent to the MER instruments except without flight qualified components and no reference channel Co-57 source. Data from analog samples were critical for identification of Mg-Fe carbonate at Gusev crater. Fiber-optic VNIR spectrometers are used to obtain CRISM-like spectral data over the range 350-2500 nm, and data for Fephyllosilicates show irreversible behavior in the electronic transition region upon dessication. The MB and VNIR instruments can be operated within chambers where, for example, the absolute H2O concentration can be measured and controlled. Phoenix's TEGA consisted of a calorimeter coupled to a mass spectrometer (MS). The JSC laboratory testbed instrument consisted of a differential scanning calorimeter (DSC) coupled to a MS configured to operate under total pressure (12 mbar), heating rate (20 C/min), and purge gas composition (N2) analogous to the flight TEGA. TEGA detected CO2 release at both low (400-680 C) and high (725-820 C) temperature and an endothermic reaction in concert with the high temperature release. The high-temperature thermal decomposition is consistent with calcite, dolomite, or ankerite, (3-6 wt.%) or any combination of these phase based upon laboratory testbed experiments. Recent laboratory experiments suggest that the low temperature CO2 release was caused by a reaction between calcium carbonate and hydrated magnesium perchlorate; although, CO2 release by the oxidation of organic materials and Fe-/Mg-rich carbonates cannot be ruled out. MSL landed in Gale crater on August 5, 2012. Although numerous analog samples have been analyzed on the JSC laboratory testbeds, no SAM, CheMin, or ChemCam analyses have been acquired by MSL to date. The JSC SAM laboratory testbed consists of a thermal analyzer coupled with a MS configured to operate under total pressure (30 mbar), heating rate (35 C/min), and purge gas composition (He) analogous to the flight SAM. The CheMin and ChemCam laboratory testbeds were developed and built by inXitu, Inc. and Los Alamos National Laboratory, respectively, to acquire datasets relevant to the MSL CheMin and ChemCam flight instruments.

Ming, D. W.↗

The Mineralogical and Chemical Case for Habitability at Yellowknife Bay, Gale Crater, Mars

Sediments of the Yellowknife Bay formation (Gale crater) include the Sheepbed member, a mudstone cut by light-toned veins. Two drill samples, John Klein and Cumberland, were collected and analyzed by the CheMin XRD/XRF instrument and the Sample Analysis at Mars (SAM) evolved gas and isotopic analysis suite of instruments. Drill cuttings were also analyzed by the Alpha Particle X-ray Spectrometer (APXS) for bulk composition. The CheMin XRD analysis shows that the mudstone contains basaltic minerals (Fe-forsterite, augite, pigeonite, plagioclase), as well as Fe-oxide/hydroxides, Fe-sulfides, amorphous materials, and trioctahedral phyllosilicates. SAM evolved gas analysis of higher-temperature OH matches the CheMin XRD estimate of ~20% clay minerals in the mudstone. The light-toned veins contain Ca-sulfates; anhydrite and bassanite are detected by XRD but gypsum is also indicated from Mastcam spectral mapping. These sulfates appear to be almost entirely restricted to late-diagenetic veins. The sulfate content of the mudstone matrix itself is lower than other sediments analyzed on Mars. The presence of phyllosilicates indicates that the activity of water was high during their formation and/or transport and deposition (should they have been detrital). Lack of chlorite places limits on the maximum temperature of alteration (likely <100 C). The presence of Ca-sulfates rather than Mg- or Fe-sulfates suggests that the pore water pH was near-neutral and of relatively low ionic strength (although x-ray amorphous Mg-and Fe- sulfates could be present and undetectable by CheMin). The presence of Fe and S in both reduced and oxidized states represents chemical disequilibria that could have been utilized by chemolithoautotrophic biota, if present. When compared to the nearby Rocknest sand shadow mineralogy or the normative mineralogy of Martian soil, both John Klein and Cumberland exhibit a near-absence of olivine and a surplus of magnetite (7-9% of the crystalline component). The magnetite is interpreted as an authigenic product formed when olivine was altered to phyllosilicate. Saponitization of olivine (a process analogous to serpentinization) could have produced H2 in situ. Indeed, early diagenetic hollow nodules ("minibowls") present in the Cumberland mudstone are interpreted by some as forming when gas bubbles accumulated in the unconsolidated mudstone. Lastly, all of these early diagenetic features appear to have been preserved with minimal alteration since their formation, as indicated by the ease of drilling (weak lithification, lack of cementing phases), the presence of 20-30% amorphous material, and the late-stage fracturing with emplacement of calcium sulfate veins and minibowl infills, where they were intersected by veins. A rough estimate of the minimum duration of the lacustrine environment is provided by the minimum thickness of the Sheepbed member. Given 1.5 meters, and applying a mean sediment accumulation rate for lacustrine strata of 1 m/1000 yrs yields a duration of 1,500 years. If the aqueous environments represented by overlying strata are considered, such as Gillespie Lake and Shaler, then this duration increases. The Sheepbed mudstone meets all the requirements of a habitable environment: Aqueous deposition at clement conditions of P, T, pH, Eh and ionic strength, plus the availability of sources of chemical energy.

Blake, David Frederick↗

Mineralogical Results from the Mars Science Laboratory Rover Curiosity

NASA's CheMin instrument, the first X-ray Diffractometer flown in space, has been operating on Mars for nearly five years. CheMin was first to establish the quantitative mineralogy of the Mars global soil (1). The instrument was next used to determine the mineralogy of a 3.7 billion year old lacustrine mudstone, a result that, together with findings from other instruments on the MSL Curiosity rover, documented the first habitable environment found on another planet (2). The mineralogy of this mudstone from an ancient playa lake was also used to derive the maximum concentration of CO2 in the early Mars atmosphere, a surprisingly low value that calls into question the current theory that CO2 greenhouse warming was responsible for the warm and wet environment of early Mars. CheMin later identified the mineral tridymite, indicative of silica-rich volcanism, in mudstones of the Murray formation on Mt. Sharp. This discovery challenges the paradigm of Mars as a basaltic planet and ushers in a new chapter of comparative terrestrial planetology (3). CheMin is now being used to systematically sample the sedimentary layers that comprise the lower strata of Mt. Sharp, a 5,000 meter sequence of sedimentary rock laid down in what was once a crater lake, characterizing isochemical sediments that through their changing mineralogy, document the oxidation and drying out of the Mars in early Hesperian time.

Mars mineralogy↗

Using Mineralogy to Interpret Martian Geologic History

The surface mineralogy of Mars is key to interpreting the planet’s geologic history and constraining when and where Mars may have been habitable to microbial life. Orbital mineralogical data from infrared spectrometers collected over the last two decades have demonstrated that Mars is more than a basaltic planet. Thermal infrared (TIR) emission spectrometers have identified regional variations in igneous minerals, iron oxides, and chloride salts, showing evidence for magmatic evolution and aqueous alteration. Orbital visible/shortwave infrared reflectance spectra provide detailed information about the aqueous history of Mars through the identification of clay minerals, sulfates, carbonates, zeolites, and amorphous materials in ancient ~3-4-billion-year-old terrains. Mineralogical data from rovers allow us to better characterize mineral formation mechanisms by identifying mineral assemblages and placing them in geologic context using outcrop- to grain-scale images. TIR and Mössbauer data from the Mars Exploration Rovers helped identify an ancient dune-interdune playa environment with multiple episodes of groundwater at Meridiani Planum and volcanism-induced hydrothermalism at Gusev crater. The CheMin X-ray diffractometer on the Mars Science Laboratory Curiosity rover in Gale crater is the first fully quantitative mineralogical instrument sent to another planetary surface. CheMin data allow the quantification of minerals and X-ray amorphous materials with a mineral detection limit of <1 wt.% and provide crystal chemistry of major phases from refined unit-cell parameters. CheMin has revealed local mineralogical changes in ancient sedimentary rocks not seen from orbit and helped identify habitable environments. Throughout the 600+ m of vertical stratigraphy studied so far, changes in clay mineralogy, Fe-oxides/oxyhydroxides, sulfates, and carbonates demonstrate a long history of surface and groundwater at Gale crater with variable salinity, pH, Eh, and temperature. Recent CheMin data document a decrease in clay minerals and an increase in sulfate minerals in younger strata that corresponds with a change from fluvio-lacustrine to eolian depositional environments, potentially documenting a change to a drier climate across the planet.

E. B. Rampe↗

Evolved Gas Analysis and X-Ray Diffraction of Carbonate Samples from the 2009 Arctic Mars Analog Svalbard Expedition: Implications for Mineralogical Inferences from the Mars Science Laboratory

The 2009 Arctic Mars Analog Svalbard Expedition (AMASE) investigated several geologic settings using methodologies and techniques being developed or considered for future Mars missions, such as the Mars Science Laboratory (MSL), ExoMars, and Mars Sample Return (MSR). AMASE-related research comprises both analyses conducted during the expedition and further analyses of collected samples using laboratory facilities at a variety of institutions. The Sample Analysis at Mars (SAM) instrument suite, which will be part of the Analytical Laboratory on MSL, consists of a quadrupole mass spectrometer (QMS), a gas chromatograph (GC), and a tunable laser spectrometer (TLS). An Evolved Gas Analysis Mass Spectrometer (EGA-MS) was used during AMASE to represent part of the capabilities of SAM. The other instrument included in the MSL Analytical Laboratory is CheMin, which uses X-Ray Diffraction (XRD) and X-Ray Fluorescence (XRF) to perform quantitative mineralogical characterization of samples. Field-portable versions of CheMin were used during the AMASE 2009. Here, we discuss the preliminary interpretation of EGA and XRD analyses of selected AMASE carbonate samples and implications for mineralogical interpretations from MSL. Though CheMin will be the primary mineralogical tool on MSL, SAM EGA could be used to support XRD identifications or indicate the presence of volatile-bearing minerals which may be near or below XRD detection limits. Data collected with instruments in the field and in comparable laboratory setups (e.g., the SAM breadboard) will be discussed.

McAdam, A. C.↗

Field Characterization of the Mineralogy and Organic Chemistry of Carbonates from the 2010 Arctic Mars Analog Svalbard Expedition by Evolved Gas Analysis

The 2010 Arctic Mars Analog Svalbard Expedition (AMASE) investigated two geologic settings using methodologies and techniques being developed or considered for future Mars missions, such as the Mars Science Laboratory (MSL), ExoMars, and Mars Sample Return. The Sample Analysis at Mars (SAM) [1] instrument suite, which will be on MSL, consists of a quadrupole mass spectrometer (QMS), a gas chromatograph (GC), and a tunable laser mass spectrometer (TLS); all will be applied to analyze gases created by pyrolysis of samples. During AMASE, a Hiden Evolved Gas Analysis-Mass Spectrometer (EGA-MS) system represented the EGA-MS capability of SAM. Another MSL instrument, CheMin, will use x-ray diffraction (XRD) and x-ray fluorescence (XRF) to perform quantitative mineralogical characterization of samples [e.g., 2]. Field-portable versions of CheMin were used during AMASE. AMASE 2010 focused on two sites that represented biotic and abiotic analogs. The abiotic site was the basaltic Sigurdfjell vent complex, which contains Mars-analog carbonate cements including carbonate globules which are excellent analogs for the globules in the ALH84001 martian meteorite [e.g., 3, 4]. The biotic site was the Knorringfjell fossil methane seep, which featured carbonates precipitated in a methane-supported chemosynthetic community [5]. This contribution focuses on EGA-MS analyses of samples from each site, with mineralogy comparisons to CheMin team results. The results give insight into organic content and organic-mineral associations, as well as some constraints on the minerals present.

McAdam, A. C.↗

Evolved Gas Analysis of Mars Analog Samples from the Arctic Mars Analog Svalbard Expedition: Implications for Analyses by the Mars Science Laboratory

The 2011 Arctic Mars Analog Svalbard Expedition (AMASE) investigated several geologic settings on Svalbard, using methodologies and techniques being developed or considered for future Mars missions, such as the Mars Science Laboratory (MSL). The Sample Analysis at Mars (SAM) instrument suite on MSL consists of a quadrupole mass spectrometer (QMS), a gas chromatograph (GC), and a tunable laser spectrometer (TLS), which analyze gases created by pyrolysis of samples. During AMASE, a Hiden Evolved Gas Analysis-Mass Spectrometer (EGA-MS) system represented the EGA-QMS capability of SAM. Another MSL instrument, CheMin, will use x-ray diffraction (XRD) and x-ray fluorescence (XRF) to perform quantitative mineralogical characterization of samples. Field-portable versions of CheMin were used during AMASE. AMASE 2011 sites spanned a range of environments relevant to understanding martian surface materials, processes and habitability. They included the basaltic Sverrefjell volcano, which hosts carbonate globules, cements and coatings, carbonate and sulfate units at Colletth0gda, Devonian sandstone redbeds in Bockfjorden, altered basaltic lava delta deposits at Mt. Scott Keltie, and altered dolerites and volcanics at Botniahalvoya. Here we focus on SAM-like EGA-MS of a subset of the samples, with mineralogy comparisons to CheMin team results. The results allow insight into sample organic content as well as some constraints on sample mineralogy.

McAdam, A.↗

Insights into the Sulfur Mineralogy of Martian Soil at Rocknest, Gale Crater, Enabled by Evolved Gas Analyses

The first solid samples analysed by the Chemistry and Mineralogy (CheMin) instrument and Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) consisted of < 150 m fines sieved from aeolian bedform material at a site named Rocknest. All four samples of this material analyzed by SAM s evolved gas analysis mass spectrometry (EGA-MS) released H2O, CO2, O2, and SO2 (Fig. 1), as well as H2S and possibly NO. This is the first time evolved SO2 (and evolved H2S) has been detected from thermal analysis of martian materials. The identity of these evolved gases and temperature (T) of evolution can support mineral detection by CheMin and place constraints on trace volatile-bearing phases present below the CheMin detection limit or difficult to characterize with XRD (e.g., X-ray amorphous phases). Constraints on phases responsible for evolved CO2 and O2 are detailed elsewhere [1,2,3]. Here, we focus on potential constraints on phases that evolved SO2, H2S, and H2O during thermal analysis.

McAdam, A.↗

The XRD Amorphous Component in John Klein Drill Fines at Yellowknife Bay, Gale Crater, Mars

Drill fines of mudstone (targets John Klein and Cumberland) from the Sheepbed unit at Yel-lowknife Bay were analyzed by MSL payload elements including the Chemistry and Mineralogy (CheMin), APXS (Alpha Particle X-Ray Spectrometer), and Sample Analysis at Mars (SAM) instruments. CheMin XRD results show a variety of crystalline phases including feldspar, pyroxene, olivine, oxides, oxyhydroxides, sulfates, sulfides, a tri-octahedral smectite, and XRD amorphous material. The drill fines are distinctly different from corresponding analyses of the global soil (target Rocknest) in that the mudstone samples contained detectable phyllosilicate. Here we focus on John Klein and combine CheMin and APXS data to calculate the chemical composition and concentration of the amorphous component. The chemical composition of the amorphous plus smectite component for John Klein was calculated by subtracting the abundance-weighted chemical composition of the individual XRD crystalline components from the bulk composition of John Kline as measured by APXS. The chemical composition of individual crystalline components was determined either by stoichiometry (e.g., hematite and magnetite) or from their unit cell parameters (e.g., feldspar, olivine, and pyroxene). The chemical composition of the amorphous + smectite component (approx 71 wt.% of bulk sample) and bulk chemical composition are similar. In order to calculate the chemical composition of the amorphous component, a chemical composition for the tri-octahedral smectite must be assumed. We selected two tri-octahedral smectites with very different MgO/(FeO + Fe2O3) ratios (34 and 1.3 for SapCa1 and Griffithite, respectively). Relative to bulk sample, the concentration of amorphous and smectite components are 40 and 29 wt.% for SapCa1 and 33 and 36 wt.% for Griffithite. The amount of smectite was calculated by requiring the MgO concentration to be approx 0 wt.% in the amorphous component. Griffithite is the preferred smectite because the position of its 021 diffraction peak is similar to that reported for John Klein. In both cases, the amorphous component has low SiO2 and MgO and high FeO + Fe2O3, P2O5, and SO3 concentrations relative to bulk sample. The chemical composition of the bulk drill fines and XRD crystalline, smectite, and amorphous components implies alteration of an initially basaltic material under near neutral conditions (not acid sulfate), with the sulfate incorporated later as veins of CaSO4 injected into the mudstone.

Morris, Richard V.↗

Terrestrial Analogs for Clay Minerals at Yellowknife Bay, Gale Crater, Mars

Sediments of the Sheepbed unit, Gale Crater, were analyzed by the CheMin X-ray diffraction instrument on the Curiosity Rover. The sediments consist of typical basalt minerals (Fe-forsterite, augite, pigeonite, plagioclase), as well as Fe oxide/hydroxides, Fesulfides, amorphous material, and a phyllosilicate. The phyllosilicate has a broad 001 peak at approx 1.0 nm, consistent with a poorly ordered smectite. However, in the absence of diagnostic tests possible on Earth, its identity is not clear. The position of the 06L diffraction band is generally used to distinguish dioctahedral from trioctahedral smectite, but it is beyond CheMin's range of 2 Theta. The measured position of the 02L diffraction band (approx 22.5deg 2 Theta by CheMin), implies that the smectite is trioctahedral. The exact position and shape of the 02L band is determined by the cations in the 'M' sites of the smectite; to constrain those cations, we sought analogs among terrestrial smectites, emphasizing those developed from basaltic precursors. A potential analog for the Sheepbed smectite is 'griffithite,' a variety of trioctahedral smectite in altered basalt of the Topanga formation, Griffith Park, Los Angeles. 'Griffithite' has an 02L diffraction band that is close in position and shape to that of the Sheepbed smectite, although 'griffithite' has a very sharp 001 peak, indicating a high degree of layer ordering not seen in the Sheepbed smectite. A typical chemical formula for 'griffithite,' determined by electron microprobe, is (Ca0.59 Na0.03) (Mg4.28 Fe1.83) (Si6.64 Al1.36) O20 (OH)4, normalized to Si+Al=8. This formula is consistent with a fully trioctahedral Fe-Mg smectite with Ca and Na as interlayer cations. In the Topanga basalt, four types of 'griffithite' are present: fine-grained, filling cracks and vesicles; coarse-grained, filling vesicles; coarse-grained, replacing olivine phenocrysts; and coarse-grained, replacing glassy mesostasis. The fine-grained 'griffithite' formed first, and the last three varieties may be contemporaneous. One sample shows agate (alpha- quartz) that was precipitated between the episodes of deposition of the fine-grained and coarse-grained 'griffithite.' 'Griffithite' is not unique as a possible terrestrial analog - some clay minerals from the Doushantou formation, China, have similar 02L diffraction bands, and many basalts contain smectites in vesicles and as replacements after olivine. Similar trioctahedral smectites occur also in the nakhlite martian meteorites - as veinlets and replacements of olivine. By understanding the formation of these terrestrial clays, we hope to constrain the nature and mechanism of formation of the Sheepbed clay mineral.

Treiman, Allan H↗

Mineralogy of Fluvio-Lacustrine Sediments Investigated by Curiosity During the Prime Mission: Implications for Diagenesis

The Mars Science Laboratory rover Curiosity investigated sedimentary rocks that were deposited in a diversity of fluvio-lacustrine settings. The entire science payload was employed to characterize the mineralogy and chemistry of the Sheepbed mudstone at Yellowknife Bay and the Windjana sandstone at the Kimberley. Data from the CheMin instrument, a transmission Xray diffractometer, were used to determine the quantitative mineralogy of both samples. The Sheepbed mudstone contains detrital basaltic minerals, calcium sulfates, iron oxides or hydroxides, iron sulfides, trioctahedral smectite, and amorphous material. The mineral assemblage and chemical data from APXS suggest that the trioctahedral smectite and magnetite formed authigenically as a result of alteration of olivine. The apparent lack of higher-grade phyllosilicates (e.g., illite and chlorite) and the presence of anhydrite indicate diagenesis at ~50- 80 ºC. The mineralogy of the Windjana sandstone is different than the Sheepbed mudstone. Windjana contains significant abundances of K-feldspar, low- and high-Ca pyroxenes, magnetite, phyllosilicates, and amorphous material. At least two distinct phyllosilicate phases exist: a 10 Å phase and a component that is expanded with a peak at ~11.8 Å. The identity of the expanded phase is currently unknown, but could be a smectite with interlayer H2O, and the 10 Å phase could be illite or collapsed smectite. Further work is necessary to characterize the phyllosilicates, but the presence of illite could suggest that Windjana experienced burial diagenesis. Candidates for the cementing agents include fine-grained phyllosilicates, Fe-oxides, and/or amorphous material. Interpretations of CheMin data from the Windjana sandstone are ongoing at the time of writing, but we will present an estimate of the composition of the amorphous material from mass balance calculations using the APXS bulk chemistry and quantitative mineralogy from CheMin.

Rampe, Elizabeth B.↗

Characterizing the Phyllosilicate Component of the Sheepbed Mudstone in Gale Crater, Mars Using Laboratory XRD and EGA

The Curiosity rover investigated the mineralogy of the Sheepbed mudstone member of the Yellowknife Bay formation in Gale crater. Data from the Chemistry and Mineralogy (CheMin) X-ray diffractometer (XRD) helped identify phyllosilicates in the two drilled samples, John Klein and Cumberland. These patterns showed peaks at low angles, consistent with (001) peaks in 2:1 swelling phyllosilicates [1]. Evolved gas analyses (EGA) by the Sample Analysis at Mars (SAM) instrument of these samples confirmed the presence of phyllosilicates through the release of H2O at high temperatures, consistent with dehydroxylation of octahedral OH in phyllosilicates [2]. CheMin data for the phyllosilicates at John Klein and Cumberland show that they are structurally similar in that their (02l) peaks are near 22.5 deg 2theta, suggesting both samples contain trioctahedral 2:1 phyllosilicates [1]. However, the positions of the (001) peaks differ: the phyllosilicate at John Klein has its (001) peak at 10 Angstroms, whereas the phyllosilicate at Cumberland has an (001) peak at 14 Angstroms. Such differences in (001) dspacings can be ascribed to the type of cation in the interlayer site [3]. For example, large monovalent cations (e.g., K(+)) have low hydration energies and readily lose their H2O of hydration, whereas small divalent cations (e.g., Mg(2+)) have high energies of hydration and retain H2O in the phyllosilicate interlayers [3,4]. The goal of this study is to determine whether differences in the interlayer cation composition can explain the CheMin data from John Klein and Cumberland and to use this knowledge to better understand phyllosilicate formation mechanisms.

Rampe, E. B.↗

Sulphur-bearing Compounds Detected by MSL SAM Evolved Gas Analysis of Materials from Yellowknife Bay, Gale Crater, Mars

The Sample Analysis at Mars (SAM) and Chemistry and Mineralogy (CheMin) instruments on the Mars Science Laboratory (MSL) analysed several subsamples of sample fines (<150 μm) from three sites in Yellowknife Bay, an aeolian bedform termed Rocknest (hereafter "RN") and two samples drilled from the Sheepbed mudstone at sites named John Klein ("JK") and Cumberland ("CB"). SAM's evolved gas analysis (EGA) mass spectrometry detected H2O, CO2, O2, H2, SO2, H2S, HCl, NO, OCS, CS2 and other trace gases. The identity of evolved gases and temperature (T) of evolution can support mineral detection by CheMin and place constraints on trace volatile-bearing phases present below the CheMin detection limit or difficult to characterize with XRD (e.g., X-ray amorphous phases). Here, we focus on potential constraints on phases that evolved SO2, H2S, OCS, and CS2 during thermal analysis.

McAdam, A. C.↗

Isotopic Composition of Carbon Dioxide Released from Confidence Hills Sediment as Measured by the Sample Analysis at Mars (SAM) Quadrupole Mass Spectrometer

In October 2014, the Mars Science Laboratory (MSL) "Curiosity" rover drilled into the sediment at the base of Mount Sharp in a location namsed Cionfidence Hills (CH). CH marked the fifth sample pocessed by the Sample Analysis at Mars (SAM) instrument suite since Curiosity arrived in Gale Crater, with previous analyses performed at Rocknest (RN), John Klein (JK), Cumberland (CB), and Windjana (WJ). Evolved gas analysis (EGA) of all samples has indicated H2O as well as O-, C- and S-bearing phases in the samples, often at abundances that would be below the detection limit of the CheMin instrument. By examining the temperatures at which gases are evolved from samples, SAM EGA data can help provide clues to the mineralogy of volatile-bearing phases when their identities are unclear to CheMin. SAM may also detect gases evolved from amorphous material in solid samples, which is not suitable for analysis by CheMin. Finally, the isotopic composition of these gases may suggest possible formation scenarios and relationships between phases. We will discuss C isotope ratios of CO2 evolved from the CH sample as measured with SAM's quadrupole mass spectrometer (QMS) and draw comparisons to samples previously analyzed by SAM.

Franz, H. B.↗

Mineralogy of Eolian Sands at Gale Crater

The Mars Science Laboratory rover Curiosity has been exploring outcrop and regolith in Gale crater since August 6, 2012. During this exploration, the mission has collected 10 samples for mineralogical analysis by X-ray diffraction (XRD), using the CheMin instrument. The CheMin (Chemistry and Mineralogy) instrument on the Mars Science Laboratory rover Curiosity uses a CCD detector and a Co-anode tube source to acquire both mineralogy (from the pat-tern of Co diffraction) and chemical information (from energies of fluoresced X-rays). A detailed description of CheMin is provided in [1]. As part of the rover checkout after landing, the first sample selected for analysis was an eolian sand deposit (the Rocknest "sand shadow"). This sample was selected in part to characterize unconsolidated eolian regolith, but primarily to prove performance of the scoop collection system on the rover. The focus of the mission after Rocknest was on the consolidated sediments of Gale crater, so all of the nine subsequent samples were collected by drilling into bedrock com-posed of lithified sedimentary materials, including mudstone and sandstone. No scoop samples have been collected since Rocknest, but at the time this abstract was written the mission stands poised to use the scoop again, to collect active dune sands from the Bagnold dune field. Several abstracts at this conference outline the Bagnold dune campaign and summarize preliminary results from analyses on approach to the Namib dune sampling site. In this abstract we review the mineralogy of Rocknest, contrast that with the mineralogy of local sediments, and anticipate what will be learned by XRD analysis of Bagnold dune sands.

Achilles, C. N.↗

High-Temperature, Perhaps Silicic, Volcanism on Mars Evidenced by Tridymite Detection in High-SiO2 Sedimentary Rock at Gale Crater, Mars

The Mars Science Laboratory (MSL) rover, Curiosity, has been exploring sedimentary rocks within Gale crater since landing in August, 2012. On the lower slopes of Aeolis Mons (a.k.a. Mount Sharp), drill powder was collected from a high-silica (74 wt% SiO2) outcrop named Buckskin (BK). It was a surprise to find that the Buckskin sample contained significant amounts of the relatively rare silica polymorph tridymite. We describe the setting of the Buckskin sample, the detection of tridymite by the MSL Chemistry and Mineralogy (CheMin) X-ray diffraction instrument, and detection implications. Geologic setting: The Buckskin outcrop is part of the Murray formation exposed in the Marias Pass area. The formation was previously studied by CheMin in the Pahrump Hills member [1] where three samples of drill fines were analyzed (Confidence Hills (CH), Mojave2 (MJ) and Telegraph Peak (TP) [2]). Assuming approximately horizontal bedding, the Buckskin outcrop is approx.15 m stratigraphically above the bottom of the Pahrump Hills member. Mudstone, generally characterized by fine lamination, is the dominant depositional facies [1]. Buckskin Mineralogical and Chemical Composition: The CheMin instrument and XRD pattern analysis procedures have been previously discussed [3-6]. The diffraction pattern used for quantitative XRD analysis (Fig. 1) is the sum of the first 4 of 45 diffraction images. The remaining images are all characterized by both on-ring and off-ring diffraction spots that we attributed to poor grain motion and particle clumping. Coincident with particle clumping was a significant decrease in the intensity of the tridymite diffraction peaks (Fig. 2a). The derived mineralogical composition of the crystalline component (derived from the first 4 diffraction images) is given in Table 1. The tridymite is well-crystalline and its pattern is refined as monoclinic tridymite (Fig 1). Mineral chemical compositions were derived from XRD unit cell parameters or obtained from stoichiometry. The XRD-calculated amorphous component was 50 +/- 15 wt%. We constrained the value to 60 wt% because it is the minimum value necessary to give a positive Al2O3 concentration for the amorphous component using APXS data for the post-sieve dump pile (Table 2). The amorphous component has high SiO2 (approx.77 wt%) and high anion (SO3+P2O5+Cl ~10 wt%) concentrations. Calculation shows that a cation-anion balance is achieved if the cations in the amorphous component except SiO2 and TiO2, which do not readily form salts, are assumed to be present as amorphous mixed-cation sulfates, phosphates, and chlorides (or perchlorates/ chlorates).

Morris, R. V.↗

The Amorphous Composition of Three Mudstone Samples from Gale Crater: Implications for Weathering and Diagenetic Processes on Mars

The Mars Science Laboratory rover, Curiosity, is exploring the lowermost formation of Gale crater's central mound. Within this formation, three samples named Marimba, Quela, and Sebina have been analyzed by the CheMin X-ray diffractometer and the Alpha Particle X-ray Spectrometer (APXS) to determine mineralogy and bulk elemental chemistry, respectively. Marimba and Quela were also analyzed by the SAM (Sample Analysis at Mars) instrument to characterize the type and abundance of volatile phases detected in evolved gas analyses (EGA). CheMin data show similar proportions of plagioclase, hematite, and Ca-sulfates along with a mixture of di- and trioctahedral smectites at abundances of approximately 28, approximately 16, and approximately 18 wt% for Marimba, Quela, and Sebina. Approximately 50 wt% of each mudstone is comprised of X-ray amorphous and trace crystalline phases present below the CheMin detection limit (approximately 1 wt%). APXS measurements reveal a distinct bulk elemental chemistry that cannot be attributed to the clay mineral variation alone indicating a variable amorphous phase assemblage exists among the three mudstones. To explore the amorphous component, the calculated amorphous composition and SAM EGA results are used to identify amorphous phases unique to each mudstone. For example, the amorphous fraction of Marimba has twice the FeO wt% compared to Quela and Sebina yet, SAM EGA data show no evidence for Fe-sulfates. These data imply that Fe must reside in alternate Fe-bearing amorphous phases (e.g., nanophase iron oxides, ferrihydrite, etc.). Constraining the composition, abundances, and proposed identity of the amorphous fraction provides an opportunity to speculate on the past physical, chemical, and/or diagenetic processes which produced such phases in addition to sediment sources, lake chemistry, and the broader geologic history of Gale crater.

Achilles, C. N.↗

Using Mineralogy of the Bagnold Dune Field in Gale Crater to Interpret Eolian Sediment Sorting on the Martian Surface

The Mars Science Laboratory Curiosity rover landed in Gale crater in August 2012 to characterize modern and ancient surface environments. Curiosity executed a two-phase campaign to study the morphology, activity, physical properties, and chemical and mineralogical composition of the Bagnold Dune Field, an active eolian dune field on the lower slopes of Aeolis Mons (Mount Sharp). Detectable aspects of dune sand mineralogy have been examined from orbit with the visible/short-wave infrared spectrometer CRISMand the thermal-infrared spectrometers THEMIS and TES. CRISM data demonstrate variations in plagioclase, pyroxene, and olivine abundances across the dune field. Curiosity analyzed sediments from two locations in the dune field to evaluate the causes of the mineralogical differences observed from orbit. The Gobabeb sample was collected from Namib Dune, a barchanoidal dune on the upwind margin of the dune field, and the Ogunquit Beach sample was collected from the Mount Desert Island sand patch located downwind from Namib. These samples were sieved to <150 μm and delivered to the CheMin X-ray diffraction instrument for quantitative mineralogical analysis. CRISM-derived mineralogy of the Namib Dune and Mount Desert Island and CheMin-derived mineralogy of the Gobabeb and Ogunquit Beach samples can be used in a value-added manner to interpret grain segregation at the bedform to dune-field scale and evaluate contributions from local sediment sources. Models of CRISM data demonstrate that Mount Desert Island is more enriched in olivine and less enriched in plagioclase than Namib dune, suggesting that fine-grained mafic sediments are preferentially mobilized downwind. Curiosity data indicate olivine also forms a coarse lag on the lee sides of barchanoidal dunes. Minor abundances of hematite, quartz, and anhydrite and small differences in the crystal chemistry of plagioclase and pyroxene derived from CheMin data suggest that sediments from the underlying lacustrine rocks also contribute to the Bagnold sands.

Rampe, E. B.↗