ALBERT

Description: Sedimentary rock samples heated to 860 degrees Centigrade in the SAM (Sample at Mars) instrument evolved CO2 and CO indicating the presence of organic-carbon(C) in Gale Crater materials. Martian or exogenous (meteoritic, interplanetary dust) CO2 and CO could be derived from combustion of simple organics (less than 300 degrees Centigrade), complex refractory organics/amorphous carbon (300-600 degrees Centigrade), and/or magmatic carbon (greater than 600 degrees Centigrade) as result of thermal decomposition of Gale Crater perchlorates, and sulfates present that produce O2. Oxidized organic compounds could also evolve CO2 and CO over broad temperature range (150 to 800 degrees Centigrade) and such organics are expected on Mars via exogenous sources. Alternatively, organic-C could also have been oxidized to carboxylic acids [e.g, mellitic acid (RCOOH), acetate (CH3CO2-), and oxalates (C2O42-)] by oxidative radiolytic weathering, or other oxidation processes. The presence of oxidized organics is consistent with the limited detection of reduced organic-C phases by the SAM-gas chromatography. Organic-C content as determined by CO2 and CO contents could range between 800 and 2400 parts per million C indicating that substantial organic-C component is present in Gale Crater. There are contributions from SAM background however, even in worst-case scenarios, this would only account for as much as half of the detected CO2 and CO. Nevertheless, if organic-C levels were assumed to have existed in a reduced form on ancient Mars and this was bioavailable C, then less than 1 percent of C in Gale Crater sediments could have supported an exclusively heterotrophic microbial population of 1 by 10 (sup 5) cells per gram sediment (assumes 9 by 10 (sup -7) microgram per cell and 0.5 micrograms C per microgram cell). While other essential nutrients (e.g., S and P) could be limiting, organic-C contents, may have been sufficient to support limited heterotrophic microbial populations on ancient Mars.

Description: Mineralogical and geochemical data returned by orbiters and landers over the past 15 years have substantially enhanced our understanding of the history of aqueous alteration on Mars. Here, we summarize aqueous processes that have been implied from data collected by landed missions. Mars is a basaltic planet. The geochemistry of most materials has not been extensively altered by open-system aqueous processes and have average Mars crustal compositions. There are few examples of open-system alteration, such as Gale craters Pahrump Hills mudstone. Types of aqueous alteration include (1) acid-sulfate and (2) hydrolytic (circum-neutral/alkaline pH) with varying water-to-rock ratios. Several hypotheses have been suggested for acid-sulfate alteration including (1) oxidative weathering of ultramafic igneous rocks containing sulfides; (2) sulfuric acid weathering of basaltic materials; (3) acid fog weathering of basaltic materials; and (4) near-neutral pH subsurface solutions rich in Fe (sup 2 plus) that rapidly oxidized to Fe (sup 3 plus) producing excess acidity. Meridiani Planums sulfate-rich sedimentary deposit containing jarosite is the most famous acid-sulfate environment visited on Mars, although ferric sulfate-rich soils are common in Gusev craters Columbia Hills and jarosite was recently discovered in the Pahrump Hills. An example of aqueous alteration under circum-neutral pH conditions is the formation of Fe-saponite with magnetite in situ via aqueous alteration of olivine in Gale craters Sheepbed mudstone. Circum-neutral pH, hydrothermal conditions were likely required for the formation of Mg-Fe carbonate in the Columbia Hills. Diagenetic features (e.g., spherules, fracture filled veins) indicate multiple episodes of aqueous alteration/diagenesis in most sedimentary deposits. However, low water-to-rock ratios are prominent at most sites visited by landed missions (e.g., limited water for reaction to form crystalline phases possibly resulting in large amounts of short-range ordered materials and little physical separation of primary and secondary materials). Most of the aqueous alteration appears to have occurred early in the planets history; however, minor aqueous alteration may be occurring at the surface today (e.g., thin films of water forming carbonates akin to those discovered by Phoenix).

Description: In Gale crater, the Curiosity Mars rover has climbed over 300 meters of the Murray formation from the base of the Pahrump Hills to the crest of Vera Rubin Ridge. We discuss the possibility that fine-grained mudstone of the Murray formation is a diagenetic product of sediments with a chemical and mineralogical composition similar to present-day martian soil. Typical (low Ca-sulfate) Murray samples have Na2O, Al2O3, SiO2, SO3, TiO2 and FeOT concentrations within 10% (relative) of average martian soil. These oxides constitute ~85% of each sample. The Al/Si and Ti/Si ratios of Murray samples are comparable to average martian soil but distinct from other martian geologic units. Percentage difference in P2O5, Cl, K2O, Cr2O3, MnO, Ni, Zn, Br, and Ge between soil and Murray samples generally exceed 10%, but these elements and oxides amount to less than 4% of the samples. These constituents are highly variable in Murray mudstone and may reflect mobility in fluid interactions. Large discrepancies in MgO and CaO with ~50% lower concentrations in the Murray samples (~2% absolute differences) are indicative of open-system alteration if the Murray mudstone originated from soil-like material. Mineralogically, martian soil is dominated by plagioclase feldspar, pyroxenes, and olivine with minor hematite, magnetite, and Ca-sulfate. In comparison, Murray samples generally have less feldspar and pyroxene, little to no olivine, more iron oxides and Ca-sulfates, and Fe-containing phyllosilicates. If Murray mudstone originated from a Mars soil composition, aqueous alteration could have converted olivine and pyroxenes to iron oxides and phyllosilicates. Intermixed or zoned plagioclase feldspars could have lost a larger portion of calcic constituents, consistent with susceptibility to weathering, resulting in a change from ~An55 (soil) to ~An40 (Murray). This alteration could be consistent with the major element chemistry, including the small decrease in MgO and CaO. A subsequent influx of minor/trace elements and Ca-sulfate, e.g. from groundwater, would be required. In this diagenetic scenario, the bulk of the alteration would have been nearly isochemical, suggesting limited mineral segregation and aqueous alteration during transport from the drainage basin or a significant direct aeolian contribution to the Murray sediments.

Description: Sediments of the Yellowknife Bay formation (Gale crater) include the Sheepbed member, a mudstone cut by light-toned veins. Two drill samples, John Klein and Cumberland, were collected and analyzed by the CheMin XRD/XRF instrument and the Sample Analysis at Mars (SAM) evolved gas and isotopic analysis suite of instruments. Drill cuttings were also analyzed by the Alpha Particle X-ray Spectrometer (APXS) for bulk composition. The CheMin XRD analysis shows that the mudstone contains basaltic minerals (Fe-forsterite, augite, pigeonite, plagioclase), as well as Fe-oxide/hydroxides, Fe-sulfides, amorphous materials, and trioctahedral phyllosilicates. SAM evolved gas analysis of higher-temperature OH matches the CheMin XRD estimate of ~20% clay minerals in the mudstone. The light-toned veins contain Ca-sulfates; anhydrite and bassanite are detected by XRD but gypsum is also indicated from Mastcam spectral mapping. These sulfates appear to be almost entirely restricted to late-diagenetic veins. The sulfate content of the mudstone matrix itself is lower than other sediments analyzed on Mars. The presence of phyllosilicates indicates that the activity of water was high during their formation and/or transport and deposition (should they have been detrital). Lack of chlorite places limits on the maximum temperature of alteration (likely 〈100 C). The presence of Ca-sulfates rather than Mg- or Fe-sulfates suggests that the pore water pH was near-neutral and of relatively low ionic strength (although x-ray amorphous Mg-and Fe- sulfates could be present and undetectable by CheMin). The presence of Fe and S in both reduced and oxidized states represents chemical disequilibria that could have been utilized by chemolithoautotrophic biota, if present. When compared to the nearby Rocknest sand shadow mineralogy or the normative mineralogy of Martian soil, both John Klein and Cumberland exhibit a near-absence of olivine and a surplus of magnetite (7-9% of the crystalline component). The magnetite is interpreted as an authigenic product formed when olivine was altered to phyllosilicate. Saponitization of olivine (a process analogous to serpentinization) could have produced H2 in situ. Indeed, early diagenetic hollow nodules ("minibowls") present in the Cumberland mudstone are interpreted by some as forming when gas bubbles accumulated in the unconsolidated mudstone. Lastly, all of these early diagenetic features appear to have been preserved with minimal alteration since their formation, as indicated by the ease of drilling (weak lithification, lack of cementing phases), the presence of 20-30% amorphous material, and the late-stage fracturing with emplacement of calcium sulfate veins and minibowl infills, where they were intersected by veins. A rough estimate of the minimum duration of the lacustrine environment is provided by the minimum thickness of the Sheepbed member. Given 1.5 meters, and applying a mean sediment accumulation rate for lacustrine strata of 1 m/1000 yrs yields a duration of 1,500 years. If the aqueous environments represented by overlying strata are considered, such as Gillespie Lake and Shaler, then this duration increases. The Sheepbed mudstone meets all the requirements of a habitable environment: Aqueous deposition at clement conditions of P, T, pH, Eh and ionic strength, plus the availability of sources of chemical energy.

Description: Nitrate was recently detected in Gale Crater sediments on Mars at abundances up to approximately 600 mg/kg, confirming predictions of its presence at abundances consistent with models based on impact-generated nitrate and other sources of fixed nitrogen. Terrestrial Mars analogs, Mars meteorites, and other solar system materials help establish a context for interpreting in situ nitrate measurements on Mars, particularly in relation to other cooccuring salts. We compare the relative abundance of nitrates to oxychlorine (chlorate and/or perchlorate, hereafter (per)chlorate) salts on Mars and Earth. The nitrate/(per)chlorate ratio on Mars is greater than 1, significantly lower than on Earth (nitrate/(per)chlorate greater than 10(exp.3)), suggesting not only the absence of biological activity but also different (per)chlorate formation mechanisms on Mars than on Earth.