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  1. Here, the Mars Science Laboratory rover, Curiosity, is equipped with ChemCam, a laser–induced breakdown spectroscopy (LIBS) instrument, to determine the elemental composition of nearby targets quickly and remotely. We use a laboratory sample set including prepared mixtures of basalt with systematic variation in hydrated mineral content and compositionally well–characterized, altered basaltic volcanic rocks to measure hydrogen by characterizing the H–alpha emission line in LIBS spectra under Martian environmental conditions. The H contents of all samples were independently measured using thermogravimetric analysis. We found that H peak area increases with weight percent H for our laboratory mixtures with basaltic matrices. Themore » increase is linear with weight percent H in the mixtures with structurally bound H up to about 1.25 wt.% H and then steepens for higher H–content samples, a nonlinear trend not previously reported but potentially important for characterizing high water content materials. To compensate for instrument, environmental, and target matrix–related effects on quantification of H content from the LIBS signal, we examined multiple normalization methods. The best performing methods utilize O 778– and C 248–nm emission lines. The methods return comparable results when applied to ChemCam data of H–bearing materials on Mars. The calibration and normalization methods tested here will aid in investigations of H by LIBS on Mars with ChemCam and SuperCam. Further laboratory work will aid quantification across different physical matrices and heterogeneous textures because of differences we observed in H in pelletized and natural rock samples of the same composition.« less
  2. From Sol 750 to 1550, the Curiosity rover documented >100 m thick stack of fine-grained sedimentary rocks making up part of the Murray formation, at the base of Mt Sharp, Gale crater. Here, we use data collected by the ChemCam instrument to estimate the level of chemical weathering in these sedimentary rocks. Both the Chemical Index of Alteration (CIA) and the Weathering Index Scale (WIS) indicate a progressive increase in alteration up section, reaching values of CIA of 63 and WIS of 25%. The increase in CIA and WIS values is coupled with a decrease in calcium abundance, suggesting partialmore » dissolution of Ca-bearing minerals (clinopyroxene and plagioclase). Mineralogy from the CheMin X-ray diffraction instrument indicates a decrease in mafic minerals compared with previously analyzed strata and a significant proportion of phyllosilicates consistent with this interpretation. Furthermore, these observations suggest that the sediments were predominantly altered in an open system, before or during their emplacement, contrasting with the rock-dominated conditions inferred in sedimentary deposits analyzed at Yellowknife Bay.« less
  3. Grain size in martian sedimentary rocks can be constrained using point-to-point chemical variabilities in Laser Induced Breakdown Spectroscopy (LIBS) data from the ChemCam instrument on the Mars Science Laboratory (MSL) Curiosity rover. The diameter of each point ablated by the ChemCam laser is in the range of medium to coarse sand in size. Thus, rocks with grains significantly smaller than the laser spot size produce bulk rock compositions at each LIBS point and low point-to-point chemical variability among LIBS points. In contrast, analyses of rocks with grains about the size of the spot or larger contain contributions from individual grainsmore » at each point and often have high point-to-point chemical variability. Here the Gini index, a statistical parameter, was used to calculate the point-to-point chemical variability in major-element oxide compositions derived from the ChemCam LIBS data. First, the total range of each LIBS major-element oxide composition was normalized from 0 to 1 across all LIBS observations. Then the Gini index was calculated for each oxide in each LIBS observation. Finally, the Gini indices of each oxide were averaged to derive a Gini index mean score, G MEAN, for each LIBS observation. A correlation between G MEAN and grain size was validated using sedimentary rocks of various grain sizes from the Yellowknife Bay formation and the Pahrump Hills member of the Murray formation in Gale crater. Overall, finer-grained rocks had smaller G MEAN than coarser-grained rocks. To calibrate G MEAN to grain size, grain size estimates based on visual assessment of high-resolution images were compared to G MEAN values for the same targets to create a calibrated scale. This calibrated scale was used to infer the grain size of rocks with unknown grain size. Overall, the grain sizes predicted for rocks with unknown grain size overlapped with those of known grain size from the same units and/or bedrock targets. The grain sizes inferred using the G MEAN based on ChemCam LIBS data are complimentary to those determined from images and both techniques can be used to improve interpretations of the depositional environments of rocks analyzed by Curiosity and future Mars missions with LIBS, such as the Mars 2020 rover.« less
  4. We present that alteration of the uppermost surfaces of geologic materials is a pervasive process on planetary surfaces that is dependent upon factors including parent composition and the environment under which alteration is occurring. While rapid and pervasive in hot and humid climates on Earth, chemical weathering of rock surfaces has also been found to dominate in some of Earth's coldest and driest landscapes as well. Specifically, surfaces dominated by resistant fine-grained igneous rocks in the Antarctic preserve evidence of oxidative weathering processes, which represent the initial immature surface alteration processes that stagnate due to the lack of available watermore » and kinetics necessary for the production of more mature alteration phases. In this study, we test the hypothesis that oxidative weathering also dominates the surfaces of sedimentary rocks throughout the Antarctic. We investigated the chemistry and mineralogy of a suite of sedimentary rocks from the Transantarctic Mountains ranging from fine-grained tuffs to coarse-grained sandstones and conglomerates. Additionally, our results show that, like the previously studied fine-grained igneous rocks in the Antarctic, sedimentary rocks generally showed only minor chemical weathering signatures at their surfaces relative to their interiors. However, unlike the igneous rocks in this earlier study, the sedimentary rocks exhibited a wide variety of non-systematic differences between surface and interior compositions. This variability of surface weathering signatures is equally as complex as the physical properties and compositions inherently present within these different sedimentary lithologies. Based on these analyses, it is apparent that oxidative weathering products do not dominate the surfaces of sedimentary rocks throughout the Transantarctic Mountains, which instead exhibit a wide array of weathering signatures that are likely dependent on both lithological and environmental factors. Considering that sedimentary lithologies are widespread across a significant fraction of the martian surface, our results suggest that observed alteration signatures limited to the surfaces of martian sedimentary rocks are most likely to be minor and to vary as a result of the lithological properties of the specific rock unit and not as a result of the widespread influences of the modern cold and dry climatic conditions.« less
  5. Here, the ubiquitous eolian dust on Mars plays important roles in the current sedimentary and atmospheric processes of the planet. The ChemCam instrument retrieves a consistent eolian dust composition at the sub–mm scale from every first laser shot on Mars targets. Its composition presents significant differences with the Aeolis Palus soils and the Bagnold dunes as it contains lower CaO and higher SiO 2. The dust FeO and TiO 2 contents are also higher, probably associated with nanophase oxide components. The dust spectra show the presence of volatile elements (S, Cl), and the hydrogen content is similar to Bagnold sands,more » but lower than Aeolis Palus soils. Consequently, the dust may be a contributor to the amorphous component of soils but differences in composition indicate that the two materials are not equivalent.« less
  6. Here, the SuperCam instrument suite onboard the Mars 2020 rover will include the Mars Microphone, an experiment designed to record the sounds of the SuperCam laser strikes on rocks and also aeolian noise. In order to record shock waves produced by the laser blasts, the Mars Microphone must be able to record audio signals from 100 Hz to 10 kHz on the surface of Mars, with a sensitivity sufficient to monitor a laser impact at distances up to 4 m. We have used the Aarhus planetary simulator facility to test the Mars 2020 rover microphone in a controlled Martian environment.more » The end-to-end tests performed in a 6 mbar CO 2 atmosphere, with wind, and also with the microphone at –80°C have demonstrated that the SuperCam/Mars Microphone requirements are satisfied. Tests were also performed on Martian soil simulant targets showing that the variation of the acoustic energy of the shock wave depends on the level of compaction of the target.« less
  7. Photodissociation of CO is a fundamental chemical mechanism for mass-independent oxygen isotope fractionation in the early Solar System. Branching ratios of photodissociation channels for individual bands quantitatively yield the trapping efficiencies of atomic oxygen resulting into oxides. We measured the branching ratios for the spin-forbidden and spin-allowed photodissociation channels of 12C 16O in the vacuum ultraviolet (VUV) photon energy region from 106 250 to 107 800 cm –1 using the VUV laser time-slice velocity-map imaging photoion technique. The excitations to four 1Π bands and three 1Σ + bands of 12C 16O were identified and investigated. The branching ratios for themore » product channels C( 3P) + O( 3P), C( 1D) + O( 3P), and C( 3P) + O( 1D) of these predissociative states strongly depend on the electronic and vibrational states of CO being excited. Furthermore, by plotting the branching ratio of the spin-forbidden dissociation channels versus the excitation energy from 102 500 to 110 500 cm –1 that has been measured so far, the global pattern of the 1Π– 3Π interaction that plays a key role in the predissociation of CO is revealed and discussed.« less
  8. Here, we compare element and isotopic fractionations measured in bulk solar wind samples collected by NASA's Genesis mission with those predicted from models incorporating both the ponderomotive force in the chromosphere and conservation of the first adiabatic invariant in the low corona. Generally good agreement is found, suggesting that these factors are consistent with the process of solar wind fractionation. Based on bulk wind measurements, we also consider in more detail the isotopic and elemental abundances of O. We also find mild support for an O abundance in the range 8.75–8.83, with a value as low as 8.69 disfavored. Amore » stronger conclusion must await solar wind regime-specific measurements from the Genesis samples.« less
  9. The ChemCam instrument on the Mars Science Laboratory (MSL) rover, Curiosity, observed numerous igneous float rocks and conglomerate clasts, reported previously. A new statistical analysis of single-laser-shot spectra of igneous targets observed by ChemCam shows a strong peak at ~55 wt% SiO 2 and 6 wt% total alkalis, with a minor secondary maximum at 47–51 wt% SiO 2 and lower alkali content. The centers of these distributions, together with the rock textures, indicate that many of the ChemCam igneous targets are trachybasalts, Mg# = 27 but with a secondary concentration of basaltic material, with a focus of compositions around Mg#more » = 54. We suggest that all of these igneous rocks resulted from low-pressure, olivine-dominated fractionation of Adirondack (MER) class-type basalt compositions. This magmatism has subalkaline, tholeiitic affinities. The similarity of the basalt endmember to much of the Gale sediment compositions in the first 1000 sols of the MSL mission suggests that this type of Fe-rich, relatively low-Mg#, olivine tholeiite is the dominant constituent of the Gale catchment that is the source material for the fine-grained sediments in Gale. The similarity to many Gusev igneous compositions suggests that it is a major constituent of ancient Martian magmas, and distinct from the shergottite parental melts thought to be associated with Tharsis and the Northern Lowlands. Finally, the Gale Crater catchment sampled a mixture of this tholeiitic basalt along with alkaline igneous material, together giving some analogies to terrestrial intraplate magmatic provinces.« less
  10. Here, we report the first in situ detection of boron on Mars. Boron has been detected in Gale crater at levels <0.05 wt % B by the NASA Curiosity rover ChemCam instrument in calcium-sulfate-filled fractures, which formed in a late-stage groundwater circulating mainly in phyllosilicate-rich bedrock interpreted as lacustrine in origin. We also consider two main groundwater-driven hypotheses to explain the presence of boron in the veins: leaching of borates out of bedrock or the redistribution of borate by dissolution of borate-bearing evaporite deposits. Our results suggest that an evaporation mechanism is most likely, implying that Gale groundwaters were mildlymore » alkaline. On Earth, boron may be a necessary component for the origin of life; on Mars, its presence suggests that subsurface groundwater conditions could have supported prebiotic chemical reactions if organics were also present and provides additional support for the past habitability of Gale crater.« less

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