Understanding the genesis of Martian soils is important to constrain the hydrogeologic history of the planet. Soils have the potential to record paleoenvironmental conditions, through the nature of ...secondary minerals formed during weathering. In situ X‐ray diffraction analyses in Gale crater have revealed that about one third of each soil sample is composed of amorphous materials containing hydrated phases. Here, we use the geochemical data from the ChemCam instrument to investigate the nature and origin of the hydrated amorphous phases. We report for the first time with ChemCam clues for the presence of sulfates within the amorphous component of soils. We show that sulfates are the main carrier of the soil hydration and possibly explain the nature of hydrogen and sulfur measured from orbit. These sulfates and the apparent lack of significant Al‐bearing weathering products are consistent with a model of soil formation including weathering of olivine in water‐limited acidic conditions.
Plain Language Summary
The study of Martian soils is of considerable interest as the nature of the mineral phases they contain, formed by the action of water for some of them, can give information on the past environments of the planet. Mineralogical analyses in Gale crater have shown that about one third of soils are composed of poorly crystalline materials whose nature remains unclear, and that soil hydration could be associated with these phases. Here, we use the chemical analyses from the ChemCam instrument to investigate the composition of the hydrogen‐bearing products, and we report for the first time the presence of sulfates in soils with this instrument. We demonstrate that sulfates are the main contributor to the water content of soils and are probably the source of the hydrogen and sulfur measured from orbit. The presence of sulfates and the lack of significant other secondary materials, especially enriched in aluminum, suggest that soils have probably undergone an acidic aqueous alteration with a low quantity of water, favoring the dissolution of olivine as the precursor to sulfates.
Key Points
The amorphous component of Gale crater soils contains hydrated sulfates
The Eolian dust deposits are not the carrier of the identified hydrated sulfates
Water‐limited acidic conditions may have led to the formation of these phases
Mars Science Laboratory's Sample Analysis at Mars (SAM) investigation has measured all of the stable isotopes of the heavy noble gases krypton and xenon in the martian atmosphere, in situ, from the ...Curiosity Rover at Gale Crater, Mars. Previous knowledge of martian atmospheric krypton and xenon isotope ratios has been based upon a combination of the Viking mission's krypton and xenon detections and measurements of noble gas isotope ratios in martian meteorites. However, the meteorite measurements reveal an impure mixture of atmospheric, mantle, and spallation contributions. The xenon and krypton isotopic measurements reported here include the complete set of stable isotopes, unmeasured by Viking. The new results generally agree with Mars meteorite measurements but also provide a unique opportunity to identify various non-atmospheric heavy noble gas components in the meteorites. Kr isotopic measurements define a solar-like atmospheric composition, but deviating from the solar wind pattern at 80Kr and 82Kr in a manner consistent with contributions originating from neutron capture in Br. The Xe measurements suggest an intriguing possibility that isotopes lighter than 132Xe have been enriched to varying degrees by spallation and neutron capture products degassed to the atmosphere from the regolith, and a model is constructed to explore this possibility. Such a spallation component, however, is not apparent in atmospheric Xe trapped in the glassy phases of martian meteorites.
•In situ measurement of all stable isotopes of Kr and Xe in the atmosphere of Mars.•A new benchmark for untangling the sources of Kr and Xe in SNC meteorites.•Light isotope enrichments indicate neutron-capture contributions to atmospheric Kr.•Xe isotopic elevations suggest presence of spallation and neutron-capture products.
•Martian soils are analyzed for the first time at sub millimeter scale.•Three different groups of coarse grains have been distinguished.•Fine particles seem to derive from one group of coarse ...grains.•Presence of amorphous component in fine particles and some coarse grains.•Fine particles have undergone limited interaction with water.
The ChemCam instrument onboard the Curiosity rover provides for the first time an opportunity to study martian soils at a sub-millimeter resolution. In this work, we analyzed 24 soil targets probed by ChemCam during the first 250sols on Mars. Using the depth profile capability of the ChemCam LIBS (Laser-Induced Breakdown Spectroscopy) technique, we found that 45% of the soils contained coarse grains (>500μm). Three distinct clusters have been detected: Cluster 1 shows a low SiO2 content; Cluster 2 corresponds to coarse grains with a felsic composition, whereas Cluster 3 presents a typical basaltic composition. Coarse grains from Cluster 2 have been mostly observed exposed in the vicinity of the landing site, whereas coarse grains from Clusters 1 and 3 have been detected mostly buried, and were found all along the rover traverse. The possible origin of these coarse grains was investigated. Felsic (Cluster 2) coarse grains have the same origin as the felsic rocks encountered near the landing site, whereas the origin of the coarse grains from Clusters 1 and 3 seems to be more global. Fine-grained soils (particle size<laser beam diameter which is between 300 and 500μm) show a homogeneous composition all along the traverse, different from the composition of the rocks encountered at Gale. Although they contain a certain amount of hydrated amorphous component depleted in SiO2, possibly present as a surface coating, their overall chemical homogeneity and their close-to-basaltic composition suggest limited, or isochemical alteration, and a limited interaction with liquid water. Fine particles and coarse grains from Cluster 1 have a similar composition, and the former could derive from weathering of the latter. Overall martian soils have a bulk composition between that of fine particles and coarse grains. This work shows that the ChemCam instrument provides a means to study the variability of soil composition at a scale not achievable by bulk chemical analyses.
Geochemical results are presented from Curiosity's exploration of Vera Rubin ridge (VRR), in addition to the full chemostratigraphy of the predominantly lacustrine mudstone Murray formation up to and ...including VRR. VRR is a prominent ridge flanking Aeolis Mons (informally Mt. Sharp), the central mound in Gale crater, Mars, and was a key area of interest for the Mars Science Laboratory mission. ChemCam data show that VRR is overall geochemically similar to lower‐lying members of the Murray formation, even though the top of VRR shows a strong hematite spectral signature as observed from orbit. Although overall geochemically similar, VRR is characterized by a prominent decrease in Li abundance and Chemical Index of Alteration across the ridge. This decrease follows the morphology of the ridge rather than elevation and is inferred to reflect a nondepositionally controlled decrease in clay mineral abundance in VRR rocks. Additionally, a notable enrichment in Mn above baseline levels is observed on VRR. While not supporting a single model, the results suggest that VRR rocks were likely affected by multiple episodes of postdepositional groundwater interactions that made them more erosionally resistant than surrounding Murray rocks, thus resulting in the modern‐day ridge after subsequent erosion.
Plain Language Summary
Results from the ChemCam instrument on Vera Rubin ridge (VRR) in Gale crater, Mars, are presented and compared with observations from similar rocks leading up to the ridge. VRR is a prominent ridge, flanking the central mound, Aeolis Mons, in Gale crater, Mars. The ridge attracted early attention because it displays strong iron‐oxide spectral signatures. Surprisingly, ChemCam data show that VRR rocks do not show an overall increase in iron abundance relative to the comparable bedrock analyzed for almost 300 m in elevation leading up to the ridge. While similar overall, some notable variations were observed on VRR relative to lower‐lying rocks. In particular, geochemical variations suggest a strong decrease in clay content on the ridge, above which, a notable enrichment in Mn is observed. No single geological process confidently explains all observations on the ridge. Rather, we think that VRR rocks underwent a series of interactions with groundwater that caused the rocks of VRR to become more resistant to erosion than their surroundings, thus emerging as a ridge as the rocks around them eroded. This likely implies that groundwater persisted in Gale crater even long after the disappearance of the ancient lake.
Key Points
A decrease in Li and Chemical Index of Alteration, reflecting clay mineral content, is observed across Vera Rubin ridge (VRR)
A Mn‐rich interval is observed stratigraphically above the decrease in clay mineral content on VRR
VRR likely resulted from increased induration from late‐stage fluid interactions long after the lake environment in Gale crater ceased
The Curiosity rover has been characterizing mineralogical and chemical compositions of Gale crater soils on Mars since 2012. Given its sub-millimeter scale of analysis, the ChemCam instrument is well ...suited to study the composition of soil constituents. However, the interpretation of LIBS data on soils in the martian environment is complicated by the large diversity of particle sizes (from dust to sand), combined with the unknown physical arrangement of their mineral constituents (i.e., the type of grain mixtures). For example, martian soils contain a significant amount of X-ray amorphous materials whose physical form remains unclear. In this study, we reproduced martian soil analyses in the laboratory to understand how the LIBS technique can provide specific insights into the physical and chemical properties of granular soils. For this purpose, different types of samples were studied with various ranges of grain sizes, mimicking two possible mixtures that may occur in martian soils: mechanical mixtures of two populations of grains made of distinct chemical compositions; and material forming a compositionally distinct coating at the surface of grains. Our results, also supported by in situ ChemCam data, demonstrate that both the sizes and the type of mixture of soil particles have a strong influence on the LIBS measurement. For mechanical mixtures of two populations of grains larger than 125–250 μm, the scatter of the data provides information about the chemical composition of the end-members. On the other hand, the chemistry recorded by LIBS for grains with surface coatings is fully dominated by the outer material for grains smaller than 500 μm in diameter. This is due to the small penetration depth of the laser (~0.3–1.5 μm per shot), combined with the ejection of small grains at each shot, which leads to a constant replenishment of fresh material. This experimental work will thus improve our understanding of martian soils analyzed by ChemCam, and more broadly, will benefit LIBS studies of granular materials.
•Mechanical mixtures and grain coatings were analyzed using LIBS in a martian atmosphere.•Grain size and concentration were varied to study their influences on LIBS signal.•We show that mixed grains or coatings have different effects on LIBS analyses.•We provide constraints on the distribution of the amorphous component in martian soil.
A recent upgrade to the optics configuration of a thermal source FTIR microscope equipped with a focal plane array detector has enabled rapid acquisition of high magnification spectrochemical images, ...in transmission, with an effective geometric pixel size of ∼1 × 1 μm(2) at the sample plane. Examples, including standard imaging targets for scale and accuracy, as well as biomedical tissues and microorganisms, have been imaged with the new system and contrasted with data acquired at normal magnification and with a high magnification multi-beam synchrotron instrument. With this optics upgrade, one can now conduct rapid biodiagnostic ex vivo tissue imaging in-house, with images collected over larger areas, in less time (minutes) and with comparable quality and resolution to the best synchrotron source FTIR imaging capabilities.
A remote laser-induced breakdown spectrometer (LIBS) designed to simulate the ChemCam instrument on the Mars Science Laboratory Rover Curiosity was used to probe 100 geologic samples at a 9-m ...standoff distance. ChemCam consists of an integrated remote LIBS instrument that will probe samples up to 7m from the mast of the rover and a remote micro-imager (RMI) that will record context images. The elemental compositions of 100 igneous and highly-metamorphosed rocks are determined with LIBS using three variations of multivariate analysis, with a goal of improving the analytical accuracy. Two forms of partial least squares (PLS) regression are employed with finely-tuned parameters: PLS-1 regresses a single response variable (elemental concentration) against the observation variables (spectra, or intensity at each of 6144 spectrometer channels), while PLS-2 simultaneously regresses multiple response variables (concentrations of the ten major elements in rocks) against the observation predictor variables, taking advantage of natural correlations between elements. Those results are contrasted with those from the multivariate regression technique of the least absolute shrinkage and selection operator (lasso), which is a penalized shrunken regression method that selects the specific channels for each element that explain the most variance in the concentration of that element. To make this comparison, we use results of cross-validation and of held-out testing, and employ unscaled and uncentered spectral intensity data because all of the input variables are already in the same units. Results demonstrate that the lasso, PLS-1, and PLS-2 all yield comparable results in terms of accuracy for this dataset.
However, the interpretability of these methods differs greatly in terms of fundamental understanding of LIBS emissions. PLS techniques generate principal components, linear combinations of intensities at any number of spectrometer channels, which explain as much variance in the response variables as possible while avoiding multicollinearity between principal components. When the selected number of principal components is projected back into the original feature space of the spectra, 6144 correlation coefficients are generated, a small fraction of which are mathematically significant to the regression. In contrast, the lasso models require only a small number (<24) of non-zero correlation coefficients (β values) to determine the concentration of each of the ten major elements. Causality between the positively-correlated emission lines chosen by the lasso and the elemental concentration was examined. In general, the higher the lasso coefficient (β), the greater the likelihood that the selected line results from an emission of that element. Emission lines with negative β values should arise from elements that are anti-correlated with the element being predicted. For elements except Fe, Al, Ti, and P, the lasso-selected wavelength with the highest β value corresponds to the element being predicted, e.g. 559.8nm for neutral Ca. However, the specific lines chosen by the lasso with positive β values are not always those from the element being predicted. Other wavelengths and the elements that most strongly correlate with them to predict concentration are obviously related to known geochemical correlations or close overlap of emission lines, while others must result from matrix effects. Use of the lasso technique thus directly informs our understanding of the underlying physical processes that give rise to LIBS emissions by determining which lines can best represent concentration, and which lines from other elements are causing matrix effects.
► Compositions of 100 rocks are predicted from LIBS with PLS-1, PLS-2, and the lasso. ► All yield comparable results in terms of accuracy, but not interpretability. ► Lasso chooses channels from known atomic emissions.
•First ChemCam analysis of hydrogen.•Description of data acquisition and processing for hydrogen.•Analysis of hydrogen within different clusters defined by multivariate methods.•Almost all data seems ...hydrated to a variable extent.•Results consistent with fluvial lacustrine context observed by the Curiosity rover.
One of the main advantages of ChemCam’s LIBS (Laser-Induced Breakdown Spectroscopy) instrument onboard the Curiosity rover is its potential to detect light elements such as hydrogen at fine scales, which has never been achieved on Mars. Hydrogen lines are detected in most of the data obtained within the first 320 sols of the mission at Gale crater, Mars. This work is a description of the hydrogen signal and its variability in the ChemCam LIBS spectra; it discusses the challenges of qualitative and quantitative analysis. Data acquisition and processing steps are investigated and optimized for the detection of hydrogen on Mars. Subtraction of an appropriate dark spectrum and the deconvolution of the superimposed emission of carbon from the low-pressure CO2-dominated atmosphere are particularly important. Because the intensities of hydrogen are also affected by matrix effects, the hydrogen signal was investigated within groups of targets sharing common chemical features and similar matrices. The different groups cover a variety of rock and soil compositions encountered along the traverse (calcium sulfate veins, mafic soils, felsic, Mg-rich and Fe-rich rocks) including data from both drill holes and their tailings. Almost all these targets were found to be hydrated to variable extents. Soils have systematically higher hydrogen signals than rocks and pebbles, probably as a result of their alteration. The results from rocks suggest that various alteration processes leading to their hydration have taken place, which is consistent with the fluvial lacustrine context, the diagenetic features, and the mineralogy observed by Curiosity in Yellowknife Bay.
On Mars, Laser-Induced Breakdown Spectroscopy (LIBS) as performed by the ChemCam instrument can be used to measure the hydrogen content of targets in situ, under a low pressure CO2 atmosphere. ...However, unexpected variations observed in the Martian dataset suggest an effect related to target roughness. Here, we present a series of laboratory experiments that reproduce the effect observed on Mars and explore possible causes. We show that the hydrogen peak intensity increases significantly with increasing exposure of the target surface to the LIBS plasma, and that these variations are specific to hydrogen, as other emission lines in the spectra are not affected. The increase of the signal could be related to an addition of hydrogen to the plasma due to interaction with the surrounding target surface, yet the exact physical process to explain such effect remains to be identified. More generally, this effect should be taken into account for the quantification of hydrogen in any LIBS applications where the roughness of the target is significant.
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•The LIBS hydrogen signal specifically varies near protrusions or cavities in Mars targets.•Experiments confirm variations of the LIBS hydrogen signal due to millimeter-scale surface roughness.•Careful target selection is necessary for the quantification of hydrogen by LIBS on Mars.
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