Brine-driven destruction of clay minerals in Gale crater, Mars.

Mars' sedimentary rock record preserves information on geological (and potential astrobiological) processes that occurred on the planet billions of years ago. The Curiosity rover is exploring the lower reaches of Mount Sharp, in Gale crater on Mars. A traverse from Vera Rubin ridge to Glen Torridon has allowed Curiosity to examine a lateral transect of rock strata laid down in a martian lake ~3.5 billion years ago. We report spatial differences in the mineralogy of time-equivalent sedimentary rocks <400 meters apart. These differences indicate localized infiltration of silica-poor brines, generated during deposition of overlying magnesium sulfate-bearing strata. We propose that destabilization of silicate minerals driven by silica-poor brines (rarely observed on Earth) was widespread on ancient Mars, because sulfate deposits are globally distributed.

Evidence for Multiple Diagenetic Episodes in Ancient Fluvial-Lacustrine Sedimentary Rocks in Gale Crater, Mars.

The Curiosity rover's exploration of rocks and soils in Gale crater has provided diverse geochemical and mineralogical data sets, underscoring the complex geological history of the region. We report the crystalline, clay mineral, and amorphous phase distributions of four Gale crater rocks from an 80-m stratigraphic interval. The mineralogy of the four samples is strongly influenced by aqueous alteration processes, including variations in water chemistries, redox, pH, and temperature. Localized hydrothermal events are evidenced by gray hematite and maturation of amorphous SiO2 to opal-CT. Low-temperature diagenetic events are associated with fluctuating lake levels, evaporative events, and groundwater infiltration. Among all mudstones analyzed in Gale crater, the diversity in diagenetic processes is primarily captured by the mineralogy and X-ray amorphous chemistry of the drilled rocks. Variations indicate a transition from magnetite to hematite and an increase in matrix-associated sulfates suggesting intensifying influence from oxic, diagenetic fluids upsection. Furthermore, diagenetic fluid pathways are shown to be strongly affected by unconformities and sedimentary transitions, as evidenced by the intensity of alteration inferred from the mineralogy of sediments sampled adjacent to stratigraphic contacts.

Redox stratification of an ancient lake in Gale crater, Mars.

In 2012, NASA's Curiosity rover landed on Mars to assess its potential as a habitat for past life and investigate the paleoclimate record preserved by sedimentary rocks inside the ~150-kilometer-diameter Gale impact crater. Geological reconstructions from Curiosity rover data have revealed an ancient, habitable lake environment fed by rivers draining into the crater. We synthesize geochemical and mineralogical data from lake-bed mudstones collected during the first 1300 martian solar days of rover operations in Gale. We present evidence for lake redox stratification, established by depth-dependent variations in atmospheric oxidant and dissolved-solute concentrations. Paleoclimate proxy data indicate that a transition from colder to warmer climate conditions is preserved in the stratigraphy. Finally, a late phase of geochemical modification by saline fluids is recognized.

Chemistry, mineralogy, and grain properties at Namib and High dunes, Bagnold dune field, Gale crater, Mars: A synthesis of Curiosity rover observations.

The Mars Science Laboratory Curiosity rover performed coordinated measurements to examine the textures and compositions of aeolian sands in the active Bagnold dune field. The Bagnold sands are rounded to subrounded, very fine to medium sized (~45-500 µm) with ≥6 distinct grain colors. In contrast to sands examined by Curiosity in a dust-covered, inactive bedform called Rocknest and soils at other landing sites, Bagnold sands are darker, less red, better sorted, have fewer silt-sized or smaller grains, and show no evidence for cohesion. Nevertheless, Bagnold mineralogy and Rocknest mineralogy are similar with plagioclase, olivine, and pyroxenes in similar proportions comprising >90% of crystalline phases, along with a substantial amorphous component (35% ± 15%). Yet Bagnold and Rocknest bulk chemistry differ. Bagnold sands are Si enriched relative to other soils at Gale crater, and H2O, S, and Cl are lower relative to all previously measured Martian soils and most Gale crater rocks. Mg, Ni, Fe, and Mn are enriched in the coarse-sieved fraction of Bagnold sands, corroborated by visible/near-infrared spectra that suggest enrichment of olivine. Collectively, patterns in major element chemistry and volatile release data indicate two distinctive volatile reservoirs in Martian soils: (1) amorphous components in the sand-sized fraction (represented by Bagnold) that are Si-enriched, hydroxylated alteration products and/or H2O- or OH-bearing impact or volcanic glasses and (2) amorphous components in the fine fraction (<40 µm; represented by Rocknest and other bright soils) that are Fe, S, and Cl enriched with low Si and adsorbed and structural H2O.

Mineralogy of a mudstone at Yellowknife Bay, Gale crater, Mars.

Sedimentary rocks at Yellowknife Bay (Gale crater) on Mars include mudstone sampled by the Curiosity rover. The samples, John Klein and Cumberland, contain detrital basaltic minerals, calcium sulfates, iron oxide or hydroxides, iron sulfides, amorphous material, and trioctahedral smectites. The John Klein smectite has basal spacing of ~10 angstroms, indicating little interlayer hydration. The Cumberland smectite has basal spacing at both ~13.2 and ~10 angstroms. The larger spacing suggests a partially chloritized interlayer or interlayer magnesium or calcium facilitating H2O retention. Basaltic minerals in the mudstone are similar to those in nearby eolian deposits. However, the mudstone has far less Fe-forsterite, possibly lost with formation of smectite plus magnetite. Late Noachian/Early Hesperian or younger age indicates that clay mineral formation on Mars extended beyond Noachian time.

X-ray diffraction results from Mars Science Laboratory: mineralogy of Rocknest at Gale crater.

The Mars Science Laboratory rover Curiosity scooped samples of soil from the Rocknest aeolian bedform in Gale crater. Analysis of the soil with the Chemistry and Mineralogy (CheMin) x-ray diffraction (XRD) instrument revealed plagioclase (~An57), forsteritic olivine (~Fo62), augite, and pigeonite, with minor K-feldspar, magnetite, quartz, anhydrite, hematite, and ilmenite. The minor phases are present at, or near, detection limits. The soil also contains 27 ± 14 weight percent x-ray amorphous material, likely containing multiple Fe(3+)- and volatile-bearing phases, including possibly a substance resembling hisingerite. The crystalline component is similar to the normative mineralogy of certain basaltic rocks from Gusev crater on Mars and of martian basaltic meteorites. The amorphous component is similar to that found on Earth in places such as soils on the Mauna Kea volcano, Hawaii.

Curiosity at Gale crater, Mars: characterization and analysis of the Rocknest sand shadow.

The Rocknest aeolian deposit is similar to aeolian features analyzed by the Mars Exploration Rovers (MERs) Spirit and Opportunity. The fraction of sand <150 micrometers in size contains ~55% crystalline material consistent with a basaltic heritage and ~45% x-ray amorphous material. The amorphous component of Rocknest is iron-rich and silicon-poor and is the host of the volatiles (water, oxygen, sulfur dioxide, carbon dioxide, and chlorine) detected by the Sample Analysis at Mars instrument and of the fine-grained nanophase oxide component first described from basaltic soils analyzed by MERs. The similarity between soils and aeolian materials analyzed at Gusev Crater, Meridiani Planum, and Gale Crater implies locally sourced, globally similar basaltic materials or globally and regionally sourced basaltic components deposited locally at all three locations.

Liquid water in the domain of cubic crystalline ice Ic.

Vapor-deposited amorphous water ice when warmed above the glass transition temperature (120-140 K), is a viscous liquid which exhibits a viscosity vs temperature relationship different from that of liquid water at room temperature. New studies of thin water ice films now demonstrate that viscous liquid water persists in the temperature range 140-210 K. where it coexists with cubic crystalline ice. The liquid character of amorphous water above the glass transition is demonstrated by (1) changes in the morphology of water ice films on a nonwetting surface observed in transmission electron microscopy (TEM) at around 175 K during slow warming, (2) changes in the binding energy of water molecules measured in temperature programmed desorption (TPD) studies, and (3) changes in the shape of the 3.07 micrometers absorption band observed in grazing angle reflection-absorption infrared spectroscopy (RAIRS) during annealing at high temperature. whereby the decreased roughness of the water surface is thought to cause changes in the selection rules for the excitation of O-H stretch vibrations. Because it is present over such a wide range of temperatures, we propose that this form of liquid water is a common material in nature. where it is expected to exist in the subsurface layers of comets and on the surfaces of some planets and satellites.

Crystallization of amorphous water ice in the solar system.

Electron diffraction studies of vapor-deposited water ice have characterized the dynamical structural changes during crystallization that affect volatile retention in cometary materials. Crystallization is found to occur by nucleation of small domains, while leaving a significant part of the amorphous material in a slightly more relaxed amorphous state that coexists metastably with cubic crystalline ice. The onset of the amorphous relaxation is prior to crystallization and coincides with the glass transition. Above the glass transition temperature, the crystallization kinetics are consistent with the amorphous solid becoming a "strong" viscous liquid. The amorphous component can effectively retain volatiles during crystallization if the volatile concentration is approximately 10% or less. For higher initial impurity concentrations, a significant amount of impurities is released during crystallization, probably because the impurities are trapped on the surfaces of micropores. A model for crystallization over long timescales is described that can be applied to a wide range of impure water ices under typical astrophysical conditions if the fragility factor D, which describes the viscosity behavior, can be estimated.

Probing the structure of cometary ice.

Computer simulations of bulk and vapor deposited amorphous ices are presented. The structure of the bulk low density amorphous ice is in good agreement with experiments on pressure disordered amorphous ice. Both the low density bulk ice and the vapor deposited ices exhibit strong ordering. Vapor deposition of hot (300 K) water molecules onto a cold (77 K) substrate yields less porous ices than deposition of cold (77 K) water molecules onto a cold substrate. Both vapor deposited ices are more porous than the bulk amorphous ice. The structure of bulk high density amorphous ice is only in fair agreement with experimental results. Attempts to simulate high density amorphous ice via vapor deposition were not successful. Electron diffraction results on vapor deposited amorphous ice indicate that the temperature of the nucleation of the cubic phase depends upon the amount of time between the deposition and the onset of crystallization, suggesting that freshly deposited ice layers reconstruct on times of the order of hours. The temperature dependence of the microporosity of the vapor deposited amorphous ices might affect laboratory experiments that are aimed at simulating astrophysical ices in the context of the origin of prebiotic organic material and its transport to the Earth.

Structural transitions in amorphous water ice and astrophysical implications.

Selected area electron diffraction is used to monitor structural changes of vapor-deposited water ice in vacuum during warm-up from 15 to 188 K. A progression of three amorphous forms of water ice is found with well-defined transitions. The formation of a high-density amorphous form (Iah) at 15 K is confirmed, and the transition to the more familiar low-density form (Ial) occurs gradually over the range 38 to 68 K. At 131 K, the ice transforms into a third amorphous form (Iar), which precedes the crystallization of cubic ice (Ic) and coexists metastably with Ic from 148 K until at least 188 K. These structural transformations of amorphous water ice can be used to explain hitherto anomalous properties of astrophysical ices. The structural transition from Iah to Ial is responsible for the diffusion and recombination of radicals in ultraviolet-photolyzed interstellar ices at low temperatures. The occurrence and persistence of Iar explains anomalous gas retention and gas release from water-rich ices at temperatures above 150 K.

The nanophase iron mineral(s) in Mars soil.

A series of surface-modified clays containing nanophase (np) iron oxide/oxyhydroxides of extremely small particle sizes, with total iron contents as high as found in Mars soil, were prepared by iron deposition on the clay surface from ferrous chloride solution. Comprehensive studies of the iron mineralogy in these "Mars-soil analogs" were conducted using chemical extractions, solubility analyses, pH and redox, x ray and electron diffractometry, electron microscopic imaging, specific surface area and particle size determinations, differential thermal analyses, magnetic properties characterization, spectral reflectance, and Viking biology simulation experiments. The clay matrix and the procedure used for synthesis produced nanophase iron oxides containing a certain proportion of divalent iron, which slowly converts to more stable, fully oxidized iron minerals. The clay acted as an effective matrix, both chemically and sterically, preventing the major part of the synthesized iron oxides from ripening, i.e., growing and developing larger crystals. The precipitated iron oxides appear as isodiametric or slightly elongated particles in the size range 1-10 nm, having large specific surface area. The noncrystalline nature of the iron compounds precipitated on the surface of the clay was verified by their complete extractability in oxalate. Lepidocrocite (gamma-FeOOH) was detected by selected area electron diffraction. It is formed from a double iron Fe(II)/Fe(III) hydroxy mineral such as "green rust," or ferrosic hydroxide. Magnetic measurements suggested that lepidocrocite converted to the more stable maghemite (gamma-Fe2O3) by mild heat treatment and then to nanophase hematite (alpha-Fe2O3) by extensive heat treatment. After mild heating, the iron-enriched clay became slightly magnetic, to the extent that it adheres to a hand-held magnet, as was observed with Mars soil. The chemical reactivity of the iron-enriched clays strongly resembles, and offers a plausible mechanism for, the somewhat puzzling observations of the Viking biology experiments. Their unique chemical reactivities are attributed to the combined catalytic effects of the iron oxide/oxyhydroxides and silicate phase surfaces. The reflectance spectrum of the clay-iron preparations in the visible range is generally similar to the reflectance curves of bright regions on Mars. This strengthens the evidence for the predominance of nanophase iron oxides/oxyhydroxides in Mars soil. The mode of formation of these nanophase iron oxides on Mars is still unknown. It is puzzling that despite the long period of time since aqueous weathering took place on Mars, they have not developed from their transitory stage to well-crystallized end-members. The possibility is suggested that these phases represent a continuously on-going, extremely slow weathering process.

The nature and origin of interstellar diamond.

Microscopic diamond was recently discovered in oxidized acid residues from several carbonaceous chondrite meteorites (for example, the C delta component of the Allende meteorite). Some of the reported properties of C delta seem in conflict with those expected of diamond. Here we present high spatial resolution analytical data which may help to explain such results. The C delta diamond is an extremely fine-grained (0.5-10 nm) single-phase material, but surface and interfacial carbon atoms, which may comprise as much as 25% of the total, impart an 'amorphous' character to some spectral data. These data support the proposed high-pressure conversion of amorphous carbon and graphite into diamonds due to grain-grain collisions in the interstellar medium although a low-pressure mechanism of formation cannot be ruled out.

A statistical method for the analysis of quantitative thin-film X-ray microanalytical data.

A series of equations is presented through which thin-film X-ray microanalytical data may be characterized statistically. Test statistics based on the Gaussian distribution are than presented, together with examples of the use and evaluation of an empirically derived Mg/Ca working curve.

Biomineralization on crinoid echinoderms. Characterization of crinoid skeletal elements using TEM and STEM microanalysis.

Columnals of Neocrinus blakei, a modern species of stalked crinoid, were studied using a variety of analytical techniques. Analyses of the magnesium calcite of the crinoid stereom using powder X-ray diffraction and electron microprobe analysis yield a composition of Ca 88Mg 12C03. Scanning transmission electron microscopy (STEM) microanalytical data indicate that Mg incorporation into the calcite structure of the crinoid stereom is random and homogeneous to at least the 20 nm level. There appear to be no variations in composition at this level either within or between structural entities of the crinoid columnal stereom. TEM reveals a heterogeneity of contrast which may be due to incorporation of organic material or some other substance which is non-crystalline in character. Single-crystal X-ray diffraction data indicate that the individual skeletal plates are single crystals which yield diffuse and imperfect X-ray reflections due to a mosaic structure. Subsequent selected area electron diffraction (SAD) photographs via TEM, using various sizes of SAD apertures, indicate that the crystallites making up the mosaic structure are (order of magnitude) about 1.0 micrometer in size. The presence of mosaic structure in the single crystal skeletal elements may at least in part explain the lack of cleavage in fracture surfaces of echinoderm skeletal material. Based on these data, as well as data from skeletal elements of other deep water, stalked crinoids, we feel that these results may be applicable to crinoids in general, at least those existing in relatively constant temperature environments. The single-crystal nature of crinoid high magnesium calcite, and its remarkable homogeneity of composition suggest that a large "vital effect" (i. e., biologic control of skeletal deposition) mediates the mineralization process.