S. M. Clegg

Elemental Geochemistry of Sedimentary Rocks at Yellowknife Bay, Gale Crater, Mars.

Sedimentary rocks examined by the Curiosity rover at Yellowknife Bay, Mars, were derived from sources that evolved from an approximately average martian crustal composition to one influenced by alkaline basalts. No evidence of chemical weathering is preserved, indicating arid, possibly cold, paleoclimates and rapid erosion and deposition. The absence of predicted geochemical variations indicates that magnetite and phyllosilicates formed by diagenesis under low-temperature, circumneutral pH, rock-dominated aqueous conditions. Analyses of diagenetic features (including concretions, raised ridges, and fractures) at high spatial resolution indicate that they are composed of iron- and halogen-rich components, magnesium-iron-chlorine–rich components, and hydrated calcium sulfates, respectively. Composition of a cross-cutting dike-like feature is consistent with sedimentary intrusion. The geochemistry of these sedimentary rocks provides further evidence for diverse depositional and diagenetic sedimentary environments during the early history of Mars.

Soil Diversity and Hydration as Observed by ChemCam at Gale Crater, Mars

The ChemCam instrument, which provides insight into martian soil chemistry at the submillimeter scale, identified two principal soil types along the Curiosity rover traverse: a fine-grained mafic type and a locally derived, coarse-grained felsic type. The mafic soil component is representative of widespread martian soils and is similar in composition to the martian dust. It possesses a ubiquitous hydrogen signature in ChemCam spectra, corresponding to the hydration of the amorphous phases found in the soil by the CheMin instrument. This hydration likely accounts for an important fraction of the global hydration of the surface seen by previous orbital measurements. ChemCam analyses did not reveal any significant exchange of water vapor between the regolith and the atmosphere. These observations provide constraints on the nature of the amorphous phases and their hydration.

Chemistry and texture of the rocks at Rocknest, Gale Crater: Evidence for sedimentary origin and diagenetic alteration

A suite of eight rocks analyzed by the Curiosity Rover while it was stopped at the Rocknest sand ripple shows the greatest chemical divergence of any potentially sedimentary rocks analyzed in the early part of the mission. Relative to average Martian soil and to the stratigraphically lower units encountered as part of the Yellowknife Bay formation, these rocks are significantly depleted in MgO, with a mean of 1.3 wt %, and high in Fe, averaging over 20 wt % FeO_T, with values between 15 and 26 wt % FeO_T. The variable iron and low magnesium and rock texture make it unlikely that these are igneous rocks. Rock surface textures range from rough to smooth, can be pitted or grooved, and show various degrees of wind erosion. Some rocks display poorly defined layering while others seem to show possible fractures. Narrow vertical voids are present in Rocknest 3, one of the rocks showing the strongest layering. Rocks in the vicinity of Rocknest may have undergone some diagenesis similar to other rocks in the Yellowknife Bay Formation as indicated by the presence of soluble calcium phases. The most reasonable scenario is that fine-grained sediments, potentially a mixture of feldspar-rich rocks from Bradbury Rise and normal Martian soil, were lithified together by an iron-rich cement.

The potassic sedimentary rocks in Gale Crater, Mars, as seen by ChemCam on board Curiosity

Key Points: • Mean K2O abundance in sedimentary rocks >5 times higher than that of the average Martian crust • Presence of alkali feldspars and K-phyllosilicates in basaltic sedimentary rocks along the traverse • The K-bearing minerals likely have a detrital origin

Chemical variations in Yellowknife Bay formation sedimentary rocks analyzed by ChemCam on board the Curiosity rover on Mars

The Yellowknife Bay formation represents a similar to 5m thick stratigraphic section of lithified fluvial and lacustrine sediments analyzed by the Curiosity rover in Gale crater, Mars. Previous works have mainly focused on the mudstones that were drilled by the rover at two locations. The present study focuses on the sedimentary rocks stratigraphically above the mudstones by studying their chemical variations in parallel with rock textures. Results show that differences in composition correlate with textures and both manifest subtle but significant variations through the stratigraphic column. Though the chemistry of the sediments does not vary much in the lower part of the stratigraphy, the variations in alkali elements indicate variations in the source material and/or physical sorting, as shown by the identification of alkali feldspars. The sandstones contain similar relative proportions of hydrogen to the mudstones below, suggesting the presence of hydrous minerals that may have contributed to their cementation. Slight variations in magnesium correlate with changes in textures suggesting that diagenesis through cementation and dissolution modified the initial rock composition and texture simultaneously. The upper part of the stratigraphy (similar to 1m thick) displays rocks with different compositions suggesting a strong change in the depositional system. The presence of float rocks with similar compositions found along the rover traverse suggests that some of these outcrops extend further away in the nearby hummocky plains.

Diagenetic silica enrichment and late‐stage groundwater activity in Gale crater, Mars

Diagenetic silica enrichment in fracture-associated halos that crosscut lacustrine and unconformably overlying aeolian sedimentary bedrock is observed on the lower north slope of Aeolis Mons in Gale crater, Mars. The diagenetic silica enrichment is colocated with detrital silica enrichment observed in the lacustrine bedrock yet extends into a considerably younger, unconformably draping aeolian sandstone, implying that diagenetic silica enrichment postdates the detrital silica enrichment. A causal connection between the detrital and diagenetic silica enrichment implies that water was present in the subsurface of Gale crater long after deposition of the lacustrine sediments and that it mobilized detrital amorphous silica and precipitated it along fractures in the overlying bedrock. Although absolute timing is uncertain, the observed diagenesis likely represents some of the most recent groundwater activity in Gale crater and suggests that the timescale of potential habitability extended considerably beyond the time that the lacustrine sediments of Aeolis Mons were deposited.

Composition of conglomerates analyzed by the Curiosity rover: Implications for Gale Crater crust and sediment sources

The Curiosity rover has analyzed various detrital sedimentary rocks at Gale Crater, among which fluvial and lacustrine rocks are predominant. Conglomerates correspond both to the coarsest sediments analyzed and the least modified by chemical alteration, enabling us to link their chemistry to that of source rocks on the Gale Crater rims. In this study, we report the results of six conglomerate targets analyzed by Alpha-Particle X-ray Spectrometer and 40 analyzed by ChemCam. The bulk chemistry derived by both instruments suggests two distinct end-members for the conglomerate compositions. The first group (Darwin type) is typical of conglomerates analyzed before sol 540; it has a felsic alkali-rich composition, with a Na2O/K2O > 5. The second group (Kimberley type) is typical of conglomerates analyzed between sols 540 and 670 in the vicinity of the Kimberley waypoint; it has an alkali-rich potassic composition with Na2O/K2O < 2. The variety of chemistry and igneous textures (when identifiable) of individual clasts suggest that each conglomerate type is a mixture of multiple source rocks. Conglomerate compositions are in agreement with most of the felsic alkali-rich float rock compositions analyzed in the hummocky plains. The average composition of conglomerates can be taken as a proxy of the average igneous crust composition at Gale Crater. Differences between the composition of conglomerates and that of finer-grained detrital sediments analyzed by the rover suggest modifications by diagenetic processes (especially for Mg enrichments in fine-grained rocks), physical sorting, and mixing with finer-grained material of different composition.

SHERLOC: Scanning habitable environments with Raman & luminescence for organics & chemicals

SHERLOC is an arm-mounted fluorescence and Raman spectrometer that was recently selected to be part of the payload for the next proposed NASA rover mission to Mars, scheduled for launch in 2020. SHERLOC enables non-contact, spatially resolved, high sensitivity detection and characterization of organics and minerals on the Martian surface. The investigation goals are to assess past aqueous history, detect the presence and preservation potential of biosignatures, and support the selection of samples for caching and potential return to Earth.

Characterization of LIBS emission lines for the identification of chlorides, carbonates, and sulfates in salt/basalt mixtures for the application to MSL ChemCam data: LIBS OF CL, C, S IN SALT-BASALT MIXTURES

Ancient 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 Curiositys 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.

Improved Intact Soil-Core Carbon Determination Applying Regression Shrinkage and Variable Selection Techniques to Complete Spectrum Laser-Induced Breakdown Spectroscopy (LIBS)

Laser-induced breakdown spectroscopy (LIBS) provides a potential method for rapid, in situ soil C measurement. In previous research on the application of LIBS to intact soil cores, we hypothesized that ultraviolet (UV) spectrum LIBS (200–300 nm) might not provide sufficient elemental information to reliably discriminate between soil organic C (SOC) and inorganic C (IC). In this study, using a custom complete spectrum (245–925 nm) core-scanning LIBS instrument, we analyzed 60 intact soil cores from six wheat fields. Predictive multi-response partial least squares (PLS2) models using full and reduced spectrum LIBS were compared for directly determining soil total C (TC), IC, and SOC. Two regression shrinkage and variable selection approaches, the least absolute shrinkage and selection operator (LASSO) and sparse multivariate regression with covariance estimation (MRCE), were tested for soil C predictions and the identification of wavelengths important for soil C prediction. Using complete spectrum LIBS for PLS2 modeling reduced the calibration standard error of prediction (SEP) 15 and 19% for TC and IC, respectively, compared to UV spectrum LIBS. The LASSO and MRCE approaches provided significantly improved calibration accuracy and reduced SEP 32–55% over UV spectrum PLS2 models. We conclude that (1) complete spectrum LIBS is superior to UV spectrum LIBS for predicting soil C for intact soil cores without pretreatment; (2) LASSO and MRCE approaches provide improved calibration prediction accuracy over PLS2 but require additional testing with increased soil and target analyte diversity; and (3) measurement errors associated with analyzing intact cores (e.g., sample density and surface roughness) require further study and quantification.