C. Fabre

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.

Calcium sulfate veins characterized by ChemCam/Curiosity at Gale crater, Mars

The Curiosity rover has analyzed abundant light-toned fracture-fill material within the Yellowknife Bay sedimentary deposits. The ChemCam instrument, coupled with Mastcam and ChemCam/Remote Micro Imager images, was able to demonstrate that these fracture fills consist of calcium sulfate veins, many of which appear to be hydrated at a level expected for gypsum and bassanite. Anhydrite is locally present and is found in a location characterized by a nodular texture. An intricate assemblage of veins crosses the sediments, which were likely formed by precipitation from fluids circulating through fractures. The presence of veins throughout the entire similar to 5 m thick Yellowknife Bay sediments suggests that this process occurred well after sedimentation and cementation/lithification of those sediments. The sulfur-rich fluids may have originated in previously precipitated sulfate-rich layers, either before the deposition of the Sheepbed mudstones or from unrelated units such as the sulfates at the base of Mount Sharp. The occurrence of these veins after the episodes of deposition of fluvial sediments at the surface suggests persistent aqueous activity in relatively nonacidic conditions.

Igneous mineralogy at Bradbury Rise: The first ChemCam campaign at Gale crater

Textural and compositional analyses using Chemistry Camera (ChemCam) remote microimager and laser-induced breakdown spectroscopy (LIBS) have been performed on five float rocks and coarse gravels along the first 100 m of the Curiosity traverse at Bradbury Rise. ChemCam, the first LIBS instrument sent to another planet, offers the opportunity to assess mineralogic diversity at grain-size scales (~ 100 µm) and, from this, lithologic diversity. Depth profiling indicates that targets are relatively free of surface coatings. One type of igneous rock is volcanic and includes both aphanitic (Coronation) and porphyritic (Mara) samples. The porphyritic sample shows dark grains that are likely pyroxene megacrysts in a fine-grained mesostasis containing andesine needles. Both types have magnesium-poor basaltic compositions and in this respect are similar to the evolved Jake Matijevic rock analyzed further along the Curiosity traverse both with Alpha-Particle X-ray Spectrometer and ChemCam instruments. The second rock type encountered is a coarse-grained intrusive rock (Thor Lake) showing equigranular texture with millimeter size crystals of feldspars and Fe-Ti oxides. Such a rock is not unique at Gale as the surrounding coarse gravels (such as Beaulieu) and the conglomerate Link are dominated by feldspathic (andesine-bytownite) clasts. Finally, alkali feldspar compositions associated with a silica polymorph have been analyzed in fractured filling material of Preble rock and in Stark, a putative pumice or an impact melt. These observations document magmatic diversity at Gale and describe the first fragments of feldspar-rich lithologies (possibly an anorthosite) that may be ancient crust transported from the crater rim and now forming float rocks, coarse gravel, or conglomerate clasts.

Trace element geochemistry (Li, Ba, Sr, and Rb) using Curiosity's ChemCam: Early results for Gale crater from Bradbury Landing Site to Rocknest

The ChemCam instrument package on the Mars rover, Curiosity, provides new capabilities to probe the abundances of certain trace elements in the rocks and soils on Mars using the laser-induced breakdown spectroscopy technique. We focus on detecting and quantifying Li, Ba, Rb, and Sr in targets analyzed during the first 100 sols, from Bradbury Landing Site to Rocknest. Univariate peak area models and multivariate partial least squares models are presented. Li, detected for the first time directly on Mars, is generally low ( 100 ppm and >1000 ppm, respectively. These analysis locations tend to have high Si and alkali abundances, consistent with a feldspar composition. Together, these trace element observations provide possible evidence of magma differentiation and aqueous alteration.

A detailed fluid inclusion study in silicified breccias from the Kombolgie sandstones (Northern Territory, Australia): inferences for the genesis of middle-Proterozoic unconformity-type uranium deposits

The relative chronology and detailed chemistry of paleofluids circulating at the base of the Kombolgie Sub-basin were investigated in the East Alligator River district (Northern Territory, Australia), where world-class unconformity-type uranium deposits are located. The chemistry of fluid inclusions was determined using in-situ analysis (Raman microprobe and laser-induced breakdown spectroscopy [LIBS]) and by observing the melting sequences by microthermometry. This study revealed the occurrence of three distinct fluids: (i) a sodium-rich brine that corresponds to a diagenetic fluid percolating at the bottom of the Kombolgie sandstones at a temperature close to 150±15 °C; (ii) a calcium-rich brine, probably corresponding to a residual brine in evaporitic environment that has evolved by fluid–rock interactions with the basement lithologies; and (iii) a low salinity fluid, heated in the basement, injected into the base of the sandstone cover. H2 and O2 and/or traces of CH4 were detected in the vapor phase of some fluid inclusions, especially in the low salinity ones in quartz breccia samples taken above mineralized areas. Hydraulic brecciation of the sandstone was associated with a pressure decrease favoring fluid mixing and the subsequent cementation of breccias. According to the fluid inclusion study and other geologic constrains, the minimum thickness of the Sub-Kombolgie Basin is estimated at 4 km. Drusy quartz breccias with evidence of fluid mixing are quite common at the base of the Kombolgie Basin, but not necessarily linked to U-mineralization. However, it is proposed that the presence of gases such as H2 and O2 in fluid inclusions, which results from water radiolysis, constitutes an indicator of gas linked to significant U concentrations deeper in the basement rocks.

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

The 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.

Advances in lithium analysis in solids by means of laser-induced breakdown spectroscopy: An exploratory study

Lithium is an important geochemical tracer for fluids or solids. However, because the electron microprobe cannot detect Li, variations of Li abundance at the micrometric scale are most often estimated from bulk analyses. In this study, the Li intense emission line at 670.706 nm in optical emission spectroscopy was used to perfect the analysis of Li at the micrometric scale by means of laser-induced breakdown spectroscopy (LIBS). To estimate lithium content for different geological materials, LIBS calibration of the emission line at 670.706 nm was achieved by use of synthetic glasses and natural minerals. The detection limit for this method is ∼5 ppm Li. Three applications to geological materials show the potential of LIBS for lithium determination, namely for Li-bearing minerals, melt inclusions, quartz, and associated fluid inclusions. For spodumene and petalite from granite pegmatite dikes (Portugal), the Li2O concentrations are 7.6 ± 1.6 wt% and 6.3 ± 1.3 wt%, respectively, by use of LIBS. These values agree with ion microprobe analyses, bulk analyses, or both. For eucryptite crystals, the Li concentrations are scattered because grain size is smaller than the LIBS spatial resolution (6 to 8 μm). Lithium concentrations of melt inclusions from the Streltsovka U deposit (Siberia) are in the range of 2 to 6.2 wt% (Li2O) for Li-rich daughter minerals. Lithium estimations on silicate glasses display values between 90 and 400 ppm. Lithium was also analyzed as a trace element in quartz. Transverse profiles were performed in hydrothermal barren quartz veins from the Spanish Central System (Sierra de Guadarrama). The highest Li concentrations (250 to 370 ppm) were found in specific growth bands in conjunction with the observed variation in optical cathodoluminescence intensity. Considering the fluid inclusion analysis, the source of fluid responsible to the Li enrichment in quartz is probably high-salinity fluids derived from sedimentary basins.

Palaeofluid chemistry of a single fluid event: a bulk and in-situ multi-technique analysis (LIBS, Raman Spectroscopy) of an Alpine fluid (Mont-Blanc)

Abstract The only direct evidence of palaeofluids that circulated in the crust is contained within fluid inclusions. To properly understand such processes requires the complete anion and cation analysis of the fluid inclusions, which are examples of single fluid events. This analysis is a major analytical challenge when an average inclusion ( −9 g of material. An integrated multi-technique approach has been applied to the analysis of single inclusions from the water–chloride (+CO 2 ) system. It includes, after a careful selection of the inclusion and its microthermometric study, the use of non-destructive techniques (Raman spectroscopy for Cl − content and gas ratios) followed by destructive techniques such as laser-induced breakdown spectroscopy for major element ratios, in parallel to a bulk determination using a miniaturised crush leach technique on the whole fluid population. The laser-induced breakdown spectroscopy technique was used in this study for the first time in a routine way for fluid inclusion analysis. It provided Na/K, Na/Ca and Na/Li ratios. Detection limits are low and adequate for the determination of ion concentrations in individual inclusions (10 ppm for Na and Li, 20 ppm for Ca and 750 ppm for K). The application was carried out on a single fluid event typical of Alpine retrograde metamorphism that affected the Mont-Blanc granite (Glacier du Geant, France). The fluids are mostly aqueous (H 2 O is dominant, XCl around 1 mol% with X=Na (930±90 mmol/kg H 2 O), K (135±35 mmol/kg H 2 O) Li (30±8 mmol/kg H 2 O), Ca (105±25 mmol/kg H 2 O), and small amounts of CO 2 +N 2 mol%). The reconstruction of the fluid composition, using major element ratios obtained by the laser-induced breakdown spectroscopy technique, is in good agreement with the estimate obtained by the crush leach method on the same sample that is dominated by a single fluid population. The low Na/Li and Na/K are indicative of interaction with the host rocks at high temperature, the latter being indicative of equilibrium with two alkali feldspars at the temperatures estimated for the fluid event.

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.