ChemCam Instrument Research Articles

Chemical alteration of fine-grained sedimentary rocks at Gale crater

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 partial 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. 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.

Using ChemCam LIBS data to constrain grain size in rocks on Mars: Proof of concept and application to rocks at Yellowknife Bay and Pahrump Hills, Gale crater

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 grains at each point and often have high point-to-point chemical variability. 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, GMEAN, for each LIBS observation. A correlation between GMEAN 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 GMEAN than coarser-grained rocks. To calibrate GMEAN to grain size, grain size estimates based on visual assessment of high-resolution images were compared to GMEAN 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 GMEAN 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.

Martian Eolian Dust Probed by ChemCam

AbstractThe 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 submillimeter 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 SiO2. The dust FeO and TiO2 contents are also higher, probably associated with nanophase oxide components. The dust spectra show the presence of volatile elements (S and Cl), and the hydrogen content is similar to Bagnold sands 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.

Quantitative Raman calibration of sulfate-bearing polymineralic mixtures: a S quantification in sedimentary rocks on Mars

AbstractThe NASA 2020 Mars mission is a Curiosity-type rover whose objective is to improve the knowledge of the geological and climatic evolution of Mars and to collect rock samples for return to Earth. The new rover has a payload of seven instruments including the SuperCam instrument which consists of four tools including a Raman spectrometer. This Raman device will be non-destructive and will analyse the surface remotely in order to determine the mineralogy of rocks and, by extent, to detect and quantify major elements such as sulfur. Sulfur has been detected as sulfate (Ca,Mg,Fe-sulfates) in sedimentary rocks. This element is difficult to quantify using the laser ablation tool of the ChemCam instrument on-board the Curiosity rover.We propose a Raman calibration to constrain the sulfur abundance in polymineralic mixtures. We acquired Raman signatures on binary and ternary mechanical mixtures containing Ca and Mg sulfates, mixed with natural silicate minerals supposed to be relevant to basaltic-sedimentary rocks at the surface of Mars: olivine, clinopyroxene, orthopyroxene and plagioclase. Using the Voigt function to process the Raman spectra from samples extracted from our mixtures allows us to calculate the initial proportions of our preparations of Ca and Mg sulfates. From these simulations, calibration equations have been provided allowing us to determine sulfate proportions (CaSO4and MgSO4) in a mixture with basaltic minerals. With the presented calibration, S can be quantified at a lower limit of 0.7 wt.% in Martian soil.

Lithium use among psychiatric patients–a risk factor for hypernatremia?

As part of the Mars Science Laboratory, the ChemCam instrument acquires remote laser induced breakdown spectra at distances that vary between 1.56 m and 7 m. This variation in distance affects the intensities of the measured LIBS emission lines in non-trivial ways. To determine the behavior of a LIBS emission line with distance, it is necessary to separate the effects of many parameters such as laser energy, laser spot size, target homogeneity, and optical collection efficiency. These parameters may be controlled in a laboratory on Earth but for field applications or in space this is a challenge. In this paper, we show that carefully selected ChemCam LIBS emission lines acquired from the Martian dust can be used to build an internal proxy spectroscopic standard. This in turn, allows for a direct measurement of the effects of the distance of various LIBS emission lines and hence can be used to correct ChemCam LIBS spectra for distance variations. When tested on pre-launch LIBS calibration data acquired under Martian-like conditions and with controlled and well-calibrated targets, this approach yields much improved agreement between targets observed at various distances. This work lays the foundation for future implementation of automated routines to correct ChemCam spectra for differences caused by variable distance.

A software package for rigorously calculating optical plasma spectra and automatically retrieving plasma properties

A free software package code named OPSIAL (Optical Plasma Spectral Calculation And Parameters Retrieval) for rigorously calculating optical plasma spectra and for automatically retrieving plasma parameters is presented.

Effects of univariate and multivariate regression on the accuracy of hydrogen quantification with laser-induced breakdown spectroscopy

Hydrogen (H) is a critical element to measure on the surface of Mars because its presence in mineral structures is indicative of past hydrous conditions. The Curiosity rover uses the laser-induced breakdown spectrometer (LIBS) on the ChemCam instrument to analyze rocks for their H emission signal at 656.6nm, from which H can be quantified. Previous LIBS calibrations for H used small data sets measured on standards and/or manufactured mixtures of hydrous minerals and rocks and applied univariate regression to spectra normalized in a variety of ways. However, matrix effects common to LIBS make these calibrations of limited usefulness when applied to the broad range of compositions on the Martian surface. In this study, 198 naturally-occurring hydrous geological samples covering a broad range of bulk compositions with directly-measured H content are used to create more robust prediction models for measuring H in LIBS data acquired under Mars conditions. Both univariate and multivariate prediction models, including partial least square (PLS) and the least absolute shrinkage and selection operator (Lasso), are compared using several different methods for normalization of H peak intensities. Data from the ChemLIBS Mars-analog spectrometer at Mount Holyoke College are compared against spectra from the same samples acquired using a ChemCam-like instrument at Los Alamos National Laboratory and the ChemCam instrument on Mars. Results show that all current normalization and data preprocessing variations for quantifying H result in models with statistically indistinguishable prediction errors (accuracies) ca. ±1.5weight percent (wt%) H2O, limiting the applications of LIBS in these implementations for geological studies. This error is too large to allow distinctions among the most common hydrous phases (basalts, amphiboles, micas) to be made, though some clays (e.g., chlorites with ≈12wt% H2O, smectites with 15–20wt% H2O) and hydrated phases (e.g., gypsum with ≈20wt% H2O) may be differentiated from lower-H phases within the known errors. Analyses of the H emission peak in Curiosity calibration targets and rock and soil targets on the Martian surface suggest that shot-to-shot variations of the ChemCam laser on Mars lead to variations in intensity that are comparable to those represented by the breadth of H standards tested in this study.

Basalt–trachybasalt samples in Gale Crater, Mars

AbstractThe 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% SiO2 and 6 wt% total alkalis, with a minor secondary maximum at 47–51 wt% SiO2 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# = 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. 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.

Roughness effects on the hydrogen signal in laser-induced breakdown spectroscopy

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.

In situ detection of boron by ChemCam on Mars

AbstractWe 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 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 mildly 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.

Visible to near-infrared MSL/Mastcam multispectral imaging: Initial results from select high-interest science targets within Gale Crater, Mars

The Mastcam CCD cameras on the Mars Science Laboratory Curiosity Rover each use an 8-position filter wheel in acquiring up to 1600 × 1200 pixel images. The filter set includes a broadband near-infrared cutoff filter for RGB Bayer imaging on each camera and 12 narrow-band geology filters distributed between the two cameras, spanning the wavelength range 445–1013 nm. This wavelength region includes the relatively broad charge-transfer and crystal-field absorption bands that are most commonly due to the presence of iron-bearing minerals. To identify such spectral features, sequences of images taken with identical pointings through different filters have been calibrated to relative reflectance using pre-flight calibration coefficients and in-flight measurements of an onboard calibration target. Within the first 1000 sols of the mission, Mastcam observed a spectrally diverse set of materials displaying absorption features consistent with the presence of iron-bearing silicate, iron oxide, and iron sulfate minerals. Dust-coated surfaces as well as soils possess a strong positive reflectance slope in the visible, consistent with the presence of nanophase iron oxides, which have long been considered the dominant visible-wavelength pigmenting agent in weathered martian surface materials. Fresh surfaces, such as tailings produced by the drill tool and the interiors of rocks broken by the rover wheels, are grayer in visible wavelengths than their reddish, dust-coated surfaces but possess reflectance spectra that vary considerably between sites. To understand the mineralogical basis of observed Mastcam reflectance spectra, we focus on a subset of the multispectral data set for which additional constraints on the composition of surface materials are available from other rover instruments, with an emphasis on sample sites for which detailed mineralogy is provided by the results of CheMin X-ray diffraction analyses. We also discuss the results of coordinated observations with the ChemCam instrument, whose passive mode of operation is capable of acquiring reflectance spectra over wavelengths that considerably overlap the range spanned by the Mastcam filter set (Johnson et al. 2016). Materials that show a distinct 430 nm band in ChemCam data also are observed to have a strong near-infrared absorption band in Mastcam spectral data, consistent with the presence of a ferric sulfate mineral. Long-distance Mastcam observations targeted toward the flanks of the Gale crater central mound are in agreement with both ChemCam spectra and orbital results, and in particular exhibit the spectral features of a crystalline hematite layer identified in MRO/CRISM data. Variations observed in Mastcam multi-filter images acquired to date have shown that multispectral observations can discriminate between compositionally different materials within Gale Crater and are in qualitative agreement with mineralogies from measured samples and orbital data.

Characterization of LIBS emission lines for the identification of chlorides, carbonates, and sulfates in salt/basalt mixtures for the application to MSL ChemCam data

AbstractAncient environmental conditions on Mars can be probed through the identification of minerals on its surface, including water‐deposited salts and cements dispersed in the pore space of sedimentary rocks. Laser‐induced breakdown spectroscopy (LIBS) analyses by the Martian rover Curiosity's ChemCam instrument can indicate salts, and ChemCam surveys aid in identifying and selecting sites for further, detailed in situ analyses. We performed laboratory LIBS experiments under simulated Mars conditions with a ChemCam‐like instrument on a series of mixtures containing increasing concentrations of salt in a basaltic background to investigate the potential for identifying and quantifying chloride, carbonate, and sulfate salts found only in small amounts, dispersed in bulk rock with ChemCam, rather than concentrated in veins. Data indicate that the presence of emission lines from the basalt matrix limited the number of Cl, C, and S emission lines found to be useful for quantitative analysis; nevertheless, several lines with intensities sensitive to salt concentration were identified. Detection limits for the elements based on individual emission lines ranged from ~20 wt % carbonate (2 wt % C), ~5–30 wt % sulfate (1–8 wt % S), and ~5–10 wt % chloride (3–6 wt % Cl) depending on the basaltic matrix and/or salt cation. Absolute quantification of Cl, C, and S in the samples via univariate analysis depends on the cation‐anion pairing in the salt but appears relatively independent of matrices tested, following normalization. These results are promising for tracking relative changes in the salt content of bulk rock on the Martian surface with ChemCam.

Quantification of water content by laser induced breakdown spectroscopy on Mars

Laser induced breakdown spectroscopy (LIBS), as performed by the ChemCam instrument, provides a new technique to measure hydrogen at the surface of Mars. Using a laboratory replica of the LIBS instrument onboard the Curiosity rover, different types of hydrated samples (basalts, calcium and magnesium sulfates, opals and apatites) covering a range of targets observed on Mars have been characterized and analyzed. A number of factors related to laser parameters, atmospheric conditions and differences in targets properties can affect the standoff LIBS signal, and in particular the hydrogen emission peak. Dedicated laboratory tests were run to identify a normalization of the hydrogen signal which could best compensate for these effects and enable the application of the laboratory calibration to Mars data. We check that the hydrogen signal increases linearly with water content; and normalization of the hydrogen emission peak using to oxygen and carbon emission peaks (related to the breakdown of atmospheric carbon dioxide) constitutes a robust approach. Moreover, the calibration curve obtained is relatively independent of the samples types.

Classification of igneous rocks analyzed by ChemCam at Gale crater, Mars

Several recent studies have revealed that Mars is not a simple basalt-covered planet, but has a more complex geological history. In Gale crater on Mars, the Curiosity rover discovered 59 igneous rocks. This paper focuses on their textures (acquired from the cameras such as MAHLI and MastCam) and their geochemical compositions that have been obtained using the ChemCam instrument. Light-toned crystals have been observed in most of the rocks. They correspond to feldspars ranging from andesines/oligoclases to anorthoclases and sanidines in the leucocratic vesiculated rocks. Darker crystals observed in all igneous rocks (except the leucocratic vesiculated ones) were analyzed by LIBS and mainly identified as Fe-rich pigeonites and Fe-augites. Iron oxides have been observed in all groups whereas F-bearing minerals have been detected only in few of them. From their textural analysis and their whole-rock compositions, all these 59 igneous rocks have been classified in five different groups; from primitive rocks i.e. dark aphanitic basalts/basanites, trachybasalts, tephrites and fine/coarse-grained gabbros/norites to more evolved materials i.e. porphyritic trachyandesites, leucocratic trachytes and quartz-diorites. The basalts and gabbros are found all along the traverse of the rover, whereas the felsic rocks are located before the Kimberley formation, i.e. close to the Peace Vallis alluvial fan deposits. This suggests that these alkali rocks have been transported by fluvial activity and could come from the Northern rim of the crater, and may correspond to deeper strata buried under basaltic regolith (Sautter et al., 2015). Some of the basaltic igneous rocks are surprisingly enriched in iron, presenting low Mg# similar to the nakhlite parental melt that cannot be produced by direct melting of the Dreibus and Wanke (1986) martian primitive mantle. The basaltic rocks at Gale are thus different from Gusev basalts. They could originate from different mantle reservoirs, or they could have undergone a more extensive fractional crystallization. Gale basaltic rocks could have been the parental magma of residual liquid extending into alkali field towards trachyte composition as magma fractionated under anhydrous condition on its way to the surface before sub adiabatic ascent.

Improved accuracy in quantitative laser-induced breakdown spectroscopy using sub-models

Accurate quantitative analysis of diverse geologic materials is one of the primary challenges faced by the laser-induced breakdown spectroscopy (LIBS)-based ChemCam instrument on the Mars Science Laboratory (MSL) rover. The SuperCam instrument on the Mars 2020 rover, as well as other LIBS instruments developed for geochemical analysis on Earth or other planets, will face the same challenge. Consequently, part of the ChemCam science team has focused on the development of improved multivariate analysis calibrations methods. Developing a single regression model capable of accurately determining the composition of very different target materials is difficult because the response of an element's emission lines in LIBS spectra can vary with the concentration of other elements. We demonstrate a conceptually simple “sub-model” method for improving the accuracy of quantitative LIBS analysis of diverse target materials. The method is based on training several regression models on sets of targets with limited composition ranges and then “blending” these “sub-models” into a single final result. Tests of the sub-model method show improvement in test set root mean squared error of prediction (RMSEP) for almost all cases. The sub-model method, using partial least squares (PLS) regression, is being used as part of the current ChemCam quantitative calibration, but the sub-model method is applicable to any multivariate regression method and may yield similar improvements.

ChemCam investigation of the John Klein and Cumberland drill holes and tailings, Gale crater, Mars

The ChemCam instrument on the Mars Science Laboratory rover analyzed the rock surface, drill hole walls, tailings, and unprocessed and sieved dump piles to investigate chemical variations with depth in the first two martian drill holes and possible fractionation or segregation effects of the drilling and sample processing. The drill sites are both in Sheepbed Mudstone, the lowest exposed member of the Yellowknife Bay formation. Yellowknife Bay is composed of detrital basaltic materials in addition to clay minerals and an amorphous component. The drill tailings are a mixture of basaltic sediments and diagenetic material like calcium sulfate veins, while the shots on the drill site surface and walls of the drill holes are closer to those pure end members. The sediment dumped from the sample acquisition, processing, and handling subsystem is of similar composition to the tailings; however, due to the specifics of the drilling process the tailings and dump piles come from different depths within the hole. This allows the ChemCam instrument to analyze samples representing the bulk composition from different depths. On the pre-drill surfaces, the Cumberland site has a greater amount of CaO and evidence for calcium sulfate veins, than the John Klein site. However, John Klein has a greater amount of calcium sulfate veins below the surface, as seen in mapping, drill hole wall analysis, and observations in the drill tailings and dump pile. In addition, the Cumberland site does not have any evidence of variations in bulk composition with depth down the drill hole, while the John Klein site has evidence for a greater amount of CaO (calcium sulfates) in the top portion of the hole compared to the middle section of the hole, where the drill sample was collected.

Application of distance correction to ChemCam laser-induced breakdown spectroscopy measurements

Laser-induced breakdown spectroscopy (LIBS) provides chemical information from atomic, ionic, and molecular emissions from which geochemical composition can be deciphered. Analysis of LIBS spectra in cases where targets are observed at different distances, as is the case for the ChemCam instrument on the Mars rover Curiosity, which performs analyses at distances between 2 and 7.4m is not a simple task. In our previous work we showed that spectral distance correction based on a proxy spectroscopic standard created from first-shot dust observations on Mars targets ameliorates the distance bias in multivariate-based elemental-composition predictions of laboratory data. In this work, we correct an expanded set of neutral and ionic spectral emissions for distance bias in the ChemCam data set. By using and testing different selection criteria to generate multiple proxy standards, we find a correction that minimizes the difference in spectral intensity measured at two different distances and increases spectral reproducibility. When the quantitative performance of distance correction is assessed, there is improvement for SiO2, Al2O3, CaO, FeOT, Na2O, K2O, that is, for most of the major rock forming elements, and for the total major-element weight percent predicted. However, for MgO the method does not provide improvements while for TiO2, it yields inconsistent results. In addition, we have observed that many emission lines do not behave consistently with distance, evidenced from laboratory analogue measurements and ChemCam data. This limits the effectiveness of the method.

Theoretical modeling and analysis of the emission spectra of a ChemCam standard: Basalt BIR-1A

We report on efforts to perform theoretical modeling of the emission spectrum measured from a basalt sample. We compare our calculations with measurements that were made to provide standards for the ChemCam instrument on the Mars Science Laboratory. We find that to obtain good agreement between modeling and the measurement, it is necessary to determine atomic and ionic level populations via a multi-element approach in which the free electron density that is created influences all the species within the plasma. Calculations that consider each element separately are found to be in poorer agreement with the measured spectrum, indicating that the ‘matrix effect’ term often used to describe the influence of other species on the emission spectrum from a given element is due to the influence of the global electron density of the plasma. We explore the emission features in both the visible and near-infrared wavelength ranges, and also examine radiation transport effects for some of the most intense features found in the basalt spectrum. Finally, we also provide comparisons of the ChemCam measurement with new high-resolution spectral measurements.

A study of machine learning regression methods for major elemental analysis of rocks using laser-induced breakdown spectroscopy

The ChemCam instrument on the Mars Curiosity rover is generating thousands of LIBS spectra and bringing interest in this technique to public attention. The key to interpreting Mars or any other types of LIBS data are calibrations that relate laboratory standards to unknowns examined in other settings and enable predictions of chemical composition. Here, LIBS spectral data are analyzed using linear regression methods including partial least squares (PLS-1 and PLS-2), principal component regression (PCR), least absolute shrinkage and selection operator (lasso), elastic net, and linear support vector regression (SVR-Lin). These were compared against results from nonlinear regression methods including kernel principal component regression (K-PCR), polynomial kernel support vector regression (SVR-Py) and k-nearest neighbor (kNN) regression to discern the most effective models for interpreting chemical abundances from LIBS spectra of geological samples. The results were evaluated for 100 samples analyzed with 50 laser pulses at each of five locations averaged together. Wilcoxon signed-rank tests were employed to evaluate the statistical significance of differences among the nine models using their predicted residual sum of squares (PRESS) to make comparisons. For MgO, SiO2, Fe2O3, CaO, and MnO, the sparse models outperform all the others except for linear SVR, while for Na2O, K2O, TiO2, and P2O5, the sparse methods produce inferior results, likely because their emission lines in this energy range have lower transition probabilities. The strong performance of the sparse methods in this study suggests that use of dimensionality-reduction techniques as a preprocessing step may improve the performance of the linear models. Nonlinear methods tend to overfit the data and predict less accurately, while the linear methods proved to be more generalizable with better predictive performance. These results are attributed to the high dimensionality of the data (6144 channels) relative to the small number of samples studied. The best-performing models were SVR-Lin for SiO2, MgO, Fe2O3, and Na2O, lasso for Al2O3, elastic net for MnO, and PLS-1 for CaO, TiO2, and K2O. Although these differences in model performance between methods were identified, most of the models produce comparable results when p≤0.05 and all techniques except kNN produced statistically-indistinguishable results. It is likely that a combination of models could be used together to yield a lower total error of prediction, depending on the requirements of the user.

Chemistry of fracture‐filling raised ridges in Yellowknife Bay, Gale Crater: Window into past aqueous activity and habitability on Mars

AbstractThe ChemCam instrument package on the Curiosity rover was used to characterize distinctive raised ridges in the Sheepbed mudstone, Yellowknife Bay formation, Gale Crater. The multilayered, fracture‐filling ridges are more resistant to erosion than the Sheepbed mudstone rock in which they occur. The bulk average composition of the raised ridges is enriched in MgO by 1.2–1.7 times (average of 8.3–11.4 wt %; single‐shot maximum of 17.0 wt %) over that of the mudstone. Al2O3 is anticorrelated with MgO, while Li is somewhat enriched where MgO is highest. Some ridges show a variation in composition with different layers on a submillimeter scale. In particular, the McGrath target shows similar high‐MgO resistant outer layers and a low‐MgO, less resistant inner layer. This is consistent with the interpretation that the raised ridges are isopachous fracture‐filling cements with a stratigraphy that likely reveals changes in fluid composition or depositional conditions over time. Overall, the average composition of the raised ridges is close to that of a Mg‐ and Fe‐rich smectite, or saponite, which may also be the main clay mineral constituent of the host mudstone. These analyses provide evidence of diagenesis and aqueous activity in the early postdepositional history of the Yellowknife Bay formation, consistent with a low salinity to brackish fluid at near‐neutral or slightly alkaline pH. The fluids that circulated through the fractures likely interacted with the Sheepbed mudstone and (or) other stratigraphically adjacent rock units of basaltic composition and leached Mg from them preferentially.