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.

Sanidine: Predicted and Observed Monoclinic-to-Triclinic Reversible Transformations at High Pressure.

High sanidine, (K,Na)AlSi(3)O(8), transforms reversibly to a triclinic phase at high pressure. This is analogous to the high-temperature monalbite transformation. Disordered alkali feldspars of various compositions have unit-cell dimensions which are very similar at the transition (a = 8.30 A, b = 12.97 A, c = 7.14 A, and beta = 116.2 degrees ), indicating that the transformation is structurally controlled. Changes in temperature, pressure, and the sodium/potassium ratio cause similar structural variations: angles between adjacent, rigid tetrahedra vary to accommodate changing effective alkali cation sizes.

Comparative Compressibilities of Silicate Spinels: Anomalous Behavior of (Mg,Fe)2SiO4.

Compressibilities of five silicate spinels, including gamma-Mg(2)SiO(4), gamma-Fe(2)SiO(4), Ni(2)SiO(4) and two ferromagnesian compositions, were determined on crystals positioned in the same high-pressure mount. Subjection of all crystals simultaneously to the same pressure revealed differences in compressibility that resulted from compositional differences. Ferromagnesian silicate spinels showed an anomalous 13 percent increase in bulk modulus with increasing iron content, from Mg(2)SiO(4) (184 gigapascals) to Fe(2)SiO(4) (207 gigapascals). This result suggests that ferrous iron and magnesium, which behave similarly under crustal conditions, are chemically more distinct at high pressures characteristic of the transition zone and lower mantle.

Zeolite Molecular Sieve 4A: Anomalous Compressibility and Volume Discontinuities at High Pressure.

Unit cell parameters of synthetic zeolite 4A were measured at several pressures to 40 kilobars with both water and an alcohol mixture as hydrostatic pressure media. Compression in water was normal, with no observed phase transitions. Compression in alcohols was twice as great as in water, and three volume discontinuities were observed. These volume changes in alcohol were rapid with increasing pressure but sluggish in reverse. High-pressure "phases," all of which are dimensionally cubic, are progressively more compressible at high pressure. These unusual high-pressure phenomena, which indicate significant interactions between zeolite 4A and the hydrostatic media, are consistent with differences in zeolite adsorption of water alcohols.

Crystal Chemistry of Silicon--Oxygen Bonds at High Pressure: Implications for the Earth's Mantle Mineralogy.

Transformations involving a change from tetrahedrally coordinated to octahedrally coordinated silicon ((IV)Si --> (VI)Si) are observed to occur at high pressure when the mean (IV)Si-O bond compresses to approximately 1.59 angstroms based on known room-pressure crystal structures, Si-O bond compressibilities, and pressures of (IV)Si --> (VI)Si transformations. The lower two-thirds of the mantle transition zone of high-density gradient (500 to 900 kilometers) corresponds to the predicted range of (IV)Si --> (VI)Si transformations. The 10 percent density increase of this zone at zero pressure is attributed primarily to the density increase associated with the change in silicon coordination. Below 900 kilometers all silicon is predicted to be in octahedral or greater coordination. The concept of cation polyhedral stability fields is defined.

Bismuth vanadate: a high-pressure, high-temperature crystallographic study of the ferroelastic-paraelastic transition.

Lattice dimensions of bismuth vanadate have been determined under 37 different high-pressure or high-temperature conditions or a combination of these conditions. New high-pressure, high-temperature, single-crystal x-ray techniques were used to bracket the reversible monoclinic (ferroelastic) to tetragonal (paraelastic) transition.

Primordial carbonylated iron-sulfur compounds and the synthesis of pyruvate.

Experiments exploring the potential catalytic role of iron sulfide at 250 degrees C and elevated pressures (50, 100, and 200 megapascals) revealed a facile, pressure-enhanced synthesis of organometallic phases formed through the reaction of alkyl thiols and carbon monoxide with iron sulfide. A suite of organometallic compounds were characterized with ultraviolet-visible and Raman spectroscopy. The natural synthesis of such compounds is anticipated in present-day and ancient environments wherever reduced hydrothermal fluids pass through iron sulfide-containing crust. Here, pyruvic acid was synthesized in the presence of such organometallic phases. These compounds could have provided the prebiotic Earth with critical biochemical functionality.

Synchrotron X-ray Diffraction Measurements of Single-Crystal Hydrogen to 26.5 Gigapascals.

The crystal structure and equation of state of solid hydrogen have been determined directly to 26.5 gigapascals at room temperature by new synchrotron x-ray diffraction techniques. Solid hydrogen remains in the hexagonal close-packed structure under these pressure-temperature conditions and exhibits increasing structural anisotropy with pressure. The pressure-volume curve determined from the x-ray data represents the most accurate experimental measurement of the equation of state to date in this pressure range. The results remove the discrepancy between earlier indirect determinations and provide a new experimental constraint on the molecular-to-atomic transition predicted at higher pressures.

An actualistic perspective into Archean worlds - (cyano-)bacterially induced sedimentary structures in the siliciclastic Nhlazatse Section, 2.9 Ga Pongola Supergroup, South Africa.

Extensive microbial mats colonize sandy tidal flats that form along the coasts of today's Earth. The microbenthos (mainly cyanobacteria) respond to the prevailing physical sediment dynamics by biostabilization, baffling and trapping, as well as binding. This biotic-physical interaction gives rise to characteristic microbially induced sedimentary structures (MISS) that differ greatly from both purely physical structures and from stromatolites. Actualistic studies of the MISS on modern tidal flats have been shown to be the key for understanding equivalent fossil structures that occur in tidal and shelf sandstones of all Earth ages. However, until now the fossil record of Archean MISS has been poor, and relatively few specimens have been found. This paper describes a study location that displays a unique assemblage with a multitude of exceptionally preserved MISS in the 2.9-Ga-old Pongola Supergroup, South Africa. The 'Nhlazatse Section' includes structures such as 'erosional remnants and pockets', 'multidirected ripple marks', 'polygonal oscillation cracks', and 'gas domes'. Optical and geochemical analyses support the biogenicity of microscopic textures such as filamentous laminae or 'orientated grains'. Textures resembling filaments are lined by iron oxide and hydroxides, as well as clay minerals. They contain organic matter, whose isotope composition is consistent with carbon of biological origin. The ancient tidal flats of the Nhlazatse Section record four microbial mat facies that occur in modern tidal settings as well. We distinguish endobenthic and epibenthic microbial mats, including planar, tufted, and spongy subtypes. Each microbial mat facies is characterized by a distinct set of MISS, and relates to a typical tidal zone. The microbial mat structures are preserved in situ, and are consistent with similar features constructed today by benthic cyanobacteria. However, other mat-constructing microorganisms also could have formed the structures in the Archean tidal flats.

Selective adsorption of L- and D-amino acids on calcite: Implications for biochemical homochirality.

The emergence of biochemical homochirality was a key step in the origin of life, yet prebiotic mechanisms for chiral separation are not well constrained. Here we demonstrate a geochemically plausible scenario for chiral separation of amino acids by adsorption on mineral surfaces. Crystals of the common rock-forming mineral calcite (CaCO(3)), when immersed in a racemic aspartic acid solution, display significant adsorption and chiral selectivity of d- and l-enantiomers on pairs of mirror-related crystal-growth surfaces. This selective adsorption is greater on crystals with terraced surface textures, which indicates that d- and l-aspartic acid concentrate along step-like linear growth features. Thus, selective adsorption of linear arrays of d- and l-amino acids on calcite, with subsequent condensation polymerization, represents a plausible geochemical mechanism for the production of homochiral polypeptides on the prebiotic Earth.

Nondestructive, in situ, cellular-scale mapping of elemental abundances including organic carbon in permineralized fossils.

The electron microprobe allows elemental abundances to be mapped at the microm scale, but until now high resolution mapping of light elements has been challenging. Modifications of electron microprobe procedure permit fine-scale mapping of carbon. When applied to permineralized fossils, this technique allows simultaneous mapping of organic material, major matrix-forming elements, and trace elements with microm-scale resolution. The resulting data make it possible to test taphonomic hypotheses for the formation of anatomically preserved silicified fossils, including the role of trace elements in the initiation of silica precipitation and in the prevention of organic degradation. The technique allows one to understand the localization of preserved organic matter before undertaking destructive chemical analyses and, because it is nondestructive, offers a potentially important tool for astrobiological investigations of samples returned from Mars or other solar system bodies.

Abiotic nitrogen reduction on the early Earth.

The production of organic precursors to life depends critically on the form of the reactants. In particular, an environment dominated by N2 is far less efficient in synthesizing nitrogen-bearing organics than a reducing environment rich in ammonia. Relatively reducing lithospheric conditions on the early Earth have been presumed to favour the generation of an ammonia-rich atmosphere, but this hypothesis has not been studied experimentally. Here we demonstrate mineral-catalysed reduction of N2, NO2- and NO3- to ammonia at temperatures between 300 and 800 degrees C and pressures of 0.1-0.4 GPa-conditions typical of crustal and oceanic hydrothermal systems. We also show that only N2 is stable above 800 degrees C, thus precluding significant atmospheric ammonia formation during hot accretion. We conclude that mineral-catalysed N2 reduction might have provided a significant source of ammonia to the Hadean ocean. These results also suggest that, whereas nitrogen in the Earth's early atmosphere was present predominantly as N2, exchange with oceanic, hydrothermally derived ammonia could have provided a significant amount of the atmospheric ammonia necessary to resolve the early-faint-Sun paradox.