Organic carbon concentrations in 3.5-billion-year-old lacustrine mudstones of Mars.

The Sample Analysis at Mars instrument stepped combustion experiment on a Yellowknife Bay mudstone at Gale crater, Mars revealed the presence of organic carbon of Martian and meteoritic origins. The combustion experiment was designed to access refractory organic carbon in Mars surface sediments by heating samples in the presence of oxygen to combust carbon to CO2. Four steps were performed, two at low temperatures (less than ∼550 °C) and two at high temperatures (up to ∼870 °C). More than 950 µg C/g was released at low temperatures (with an isotopic composition of δ13C = +1.5 ± 3.8‰) representing a minimum of 431 µg C/g indigenous organic and inorganic Martian carbon components. Above 550 °C, 273 ± 30 µg C/g was evolved as CO2 and CO (with estimated δ13C = -32.9‰ to -10.1‰ for organic carbon). The source of high temperature organic carbon cannot be definitively confirmed by isotopic composition, which is consistent with macromolecular organic carbon of igneous origin, meteoritic infall, or diagenetically altered biomass, or a combination of these. If from allochthonous deposition, organic carbon could have supported both prebiotic organic chemistry and heterotrophic metabolism at Gale crater, Mars, at ∼3.5 Ga.

Silicic volcanism on Mars evidenced by tridymite in high-SiO2 sedimentary rock at Gale crater.

Tridymite, a low-pressure, high-temperature (>870 °C) SiO2 polymorph, was detected in a drill sample of laminated mudstone (Buckskin) at Marias Pass in Gale crater, Mars, by the Chemistry and Mineralogy X-ray diffraction instrument onboard the Mars Science Laboratory rover Curiosity The tridymitic mudstone has ∼40 wt.% crystalline and ∼60 wt.% X-ray amorphous material and a bulk composition with ∼74 wt.% SiO2 (Alpha Particle X-Ray Spectrometer analysis). Plagioclase (∼17 wt.% of bulk sample), tridymite (∼14 wt.%), sanidine (∼3 wt.%), cation-deficient magnetite (∼3 wt.%), cristobalite (∼2 wt.%), and anhydrite (∼1 wt.%) are the mudstone crystalline minerals. Amorphous material is silica-rich (∼39 wt.% opal-A and/or high-SiO2 glass and opal-CT), volatile-bearing (16 wt.% mixed cation sulfates, phosphates, and chlorides-perchlorates-chlorates), and has minor TiO2 and Fe2O3T oxides (∼5 wt.%). Rietveld refinement yielded a monoclinic structural model for a well-crystalline tridymite, consistent with high formation temperatures. Terrestrial tridymite is commonly associated with silicic volcanism, and detritus from such volcanism in a "Lake Gale" catchment environment can account for Buckskin's tridymite, cristobalite, feldspar, and any residual high-SiO2 glass. These cogenetic detrital phases are possibly sourced from the Gale crater wall/rim/central peak. Opaline silica could form during diagenesis from high-SiO2 glass, as amorphous precipitated silica, or as a residue of acidic leaching in the sediment source region or at Marias Pass. The amorphous mixed-cation salts and oxides and possibly the crystalline magnetite (otherwise detrital) are primary precipitates and/or their diagenesis products derived from multiple infiltrations of aqueous solutions having variable compositions, temperatures, and acidities. Anhydrite is post lithification fracture/vein fill.

Evidence for indigenous nitrogen in sedimentary and aeolian deposits from the Curiosity rover investigations at Gale crater, Mars.

The Sample Analysis at Mars (SAM) investigation on the Mars Science Laboratory (MSL) Curiosity rover has detected oxidized nitrogen-bearing compounds during pyrolysis of scooped aeolian sediments and drilled sedimentary deposits within Gale crater. Total N concentrations ranged from 20 to 250 nmol N per sample. After subtraction of known N sources in SAM, our results support the equivalent of 110-300 ppm of nitrate in the Rocknest (RN) aeolian samples, and 70-260 and 330-1,100 ppm nitrate in John Klein (JK) and Cumberland (CB) mudstone deposits, respectively. Discovery of indigenous martian nitrogen in Mars surface materials has important implications for habitability and, specifically, for the potential evolution of a nitrogen cycle at some point in martian history. The detection of nitrate in both wind-drifted fines (RN) and in mudstone (JK, CB) is likely a result of N2 fixation to nitrate generated by thermal shock from impact or volcanic plume lightning on ancient Mars. Fixed nitrogen could have facilitated the development of a primitive nitrogen cycle on the surface of ancient Mars, potentially providing a biochemically accessible source of nitrogen.

Indication of drier periods on Mars from the chemistry and mineralogy of atmospheric dust.

The ubiquitous atmospheric dust on Mars is well mixed by periodic global dust storms, and such dust carries information about the environment in which it once formed and hence about the history of water on Mars. The Mars Exploration Rovers have permanent magnets to collect atmospheric dust for investigation by instruments on the rovers. Here we report results from Mössbauer spectroscopy and X-ray fluorescence of dust particles captured from the martian atmosphere by the magnets. The dust on the magnets contains magnetite and olivine; this indicates a basaltic origin of the dust and shows that magnetite, not maghemite, is the mineral mainly responsible for the magnetic properties of the dust. Furthermore, the dust on the magnets contains some ferric oxides, probably including nanocrystalline phases, so some alteration or oxidation of the basaltic dust seems to have occurred. The presence of olivine indicates that liquid water did not play a dominant role in the processes that formed the atmospheric dust.

Water alteration of rocks and soils on Mars at the Spirit rover site in Gusev crater.

Gusev crater was selected as the landing site for the Spirit rover because of the possibility that it once held a lake. Thus one of the rover's tasks was to search for evidence of lake sediments. However, the plains at the landing site were found to be covered by a regolith composed of olivine-rich basaltic rock and windblown 'global' dust. The analyses of three rock interiors exposed by the rock abrasion tool showed that they are similar to one another, consistent with having originated from a common lava flow. Here we report the investigation of soils, rock coatings and rock interiors by the Spirit rover from sol (martian day) 1 to sol 156, from its landing site to the base of the Columbia hills. The physical and chemical characteristics of the materials analysed provide evidence for limited but unequivocal interaction between water and the volcanic rocks of the Gusev plains. This evidence includes the softness of rock interiors that contain anomalously high concentrations of sulphur, chlorine and bromine relative to terrestrial basalts and martian meteorites; sulphur, chlorine and ferric iron enrichments in multilayer coatings on the light-toned rock Mazatzal; high bromine concentration in filled vugs and veins within the plains basalts; positive correlations between magnesium, sulphur and other salt components in trench soils; and decoupling of sulphur, chlorine and bromine concentrations in trench soils compared to Gusev surface soils, indicating chemical mobility and separation.

An integrated view of the chemistry and mineralogy of martian soils.

The mineralogical and elemental compositions of the martian soil are indicators of chemical and physical weathering processes. Using data from the Mars Exploration Rovers, we show that bright dust deposits on opposite sides of the planet are part of a global unit and not dominated by the composition of local rocks. Dark soil deposits at both sites have similar basaltic mineralogies, and could reflect either a global component or the general similarity in the compositions of the rocks from which they were derived. Increased levels of bromine are consistent with mobilization of soluble salts by thin films of liquid water, but the presence of olivine in analysed soil samples indicates that the extent of aqueous alteration of soils has been limited. Nickel abundances are enhanced at the immediate surface and indicate that the upper few millimetres of soil could contain up to one per cent meteoritic material.

Investigating the Growth of Algae Under Low Atmospheric Pressures for Potential Food and Oxygen Production on Mars.

With long-term missions to Mars and beyond that would not allow resupply, a self-sustaining Bioregenerative Life Support System (BLSS) is essential. Algae are promising candidates for BLSS due to their completely edible biomass, fast growth rates and ease of handling. Extremophilic algae such as snow algae and halophilic algae may also be especially suited for a BLSS because of their ability to grow under extreme conditions. However, as indicated from over 50 prior space studies examining algal growth, little is known about the growth of algae at close to Mars-relevant pressures. Here, we explored the potential for five algae species to produce oxygen and food under low-pressure conditions relevant to Mars. These included Chloromonas brevispina, Kremastochrysopsis austriaca, Dunaliella salina, Chlorella vulgaris, and Spirulina plantensis. The cultures were grown in duplicate in a low-pressure growth chamber at 670 ± 20 mbar, 330 ± 20 mbar, 160 ± 20 mbar, and 80 ± 2.5 mbar pressures under continuous light exposure (62-70 µmol m-2 s-1). The atmosphere was evacuated and purged with CO2 after sampling each week. Growth experiments showed that D. salina, C. brevispina, and C. vulgaris were the best candidates to be used for BLSS at low pressure. The highest carrying capacities for each species under low pressure conditions were achieved by D. salina at 160 mbar (30.0 ± 4.6 × 105 cells/ml), followed by C. brevispina at 330 mbar (19.8 ± 0.9 × 105 cells/ml) and C. vulgaris at 160 mbar (13.0 ± 1.5 × 105 cells/ml). C. brevispina, D. salina, and C. vulgaris all also displayed substantial growth at the lowest tested pressure of 80 mbar reaching concentrations of 43.4 ± 2.5 × 104, 15.8 ± 1.3 × 104, and 57.1 ± 4.5 × 104 cells per ml, respectively. These results indicate that these species are promising candidates for the development of a Mars-based BLSS using low pressure (∼200-300 mbar) greenhouses and inflatable structures that have already been conceptualized and designed.

Elevated olivine weathering rates and sulfate formation at cryogenic temperatures on Mars.

Large Hesperian-aged (~3.7 Ga) layered deposits of sulfate-rich sediments in the equatorial regions of Mars have been suggested to be evidence for ephemeral playa environments. But early Mars may not have been warm enough to support conditions similar to what occurs in arid environments on Earth. Instead cold, icy environments may have been widespread. Under cryogenic conditions sulfate formation might be blocked, since kinetics of silicate weathering are typically strongly retarded at temperatures well below 0 °C. But cryo-concentration of acidic solutions may counteract the slow kinetics. Here we show that cryo-concentrated acidic brines rapidly chemically weather olivine minerals and form sulfate minerals at temperatures as low as -60 °C. These experimental results demonstrate the viability of sulfate formation under current Martian conditions, even in the polar regions. An ice-hosted sedimentation and weathering model may provide a compelling description of the origin of large Hesperian-aged layered sulfate deposits on Mars.

Stable isotope measurements of martian atmospheric CO2 at the Phoenix landing site.

Carbon dioxide is a primary component of the martian atmosphere and reacts readily with water and silicate rocks. Thus, the stable isotopic composition of CO2 can reveal much about the history of volatiles on the planet. The Mars Phoenix spacecraft measurements of carbon isotopes [referenced to the Vienna Pee Dee belemnite (VPDB)] [delta13C(VPDB) = -2.5 +/- 4.3 per mil (per thousand)] and oxygen isotopes [referenced to the Vienna standard mean ocean water (VSMOW)] (delta18O(VSMOW) = 31.0 +/- 5.7 per thousand), reported here, indicate that CO2 is heavily influenced by modern volcanic degassing and equilibration with liquid water. When combined with data from the martian meteorites, a general model can be constructed that constrains the history of water, volcanism, atmospheric evolution, and weathering on Mars. This suggests that low-temperature water-rock interaction has been dominant throughout martian history, carbonate formation is active and ongoing, and recent volcanic degassing has played a substantial role in the composition of the modern atmosphere.

Discovery of natural perchlorate in the Antarctic Dry Valleys and its global implications.

In the past few years, it has become increasingly apparent that perchlorate (ClO(4)(-)) is present on all continents, except the polar regions where it had not yet been assessed, and that it may have a significant natural source. Here, we report on the discovery of perchlorate in soil and ice from several Antarctic Dry Valleys (ADVs) where concentrations reach up to 1100 microg/kg. In the driest ADV, perchlorate correlates with atmospherically deposited nitrate. Far from anthropogenic activity, ADV perchlorate provides unambiguous evidence that natural perchlorate is ubiquitous on Earth. The discovery has significant implications for the origin of perchlorate, its global biogeochemical interactions, and possible interactions with the polar ice sheets. The results support the hypotheses that perchlorate is produced globally and continuously in the Earth's atmosphere, that it typically accumulates in hyperarid areas, and that it does not build up in oceans or other wet environments most likely because of microbial reduction on a global scale.

Identification of carbonate-rich outcrops on Mars by the Spirit rover.

Decades of speculation about a warmer, wetter Mars climate in the planet's first billion years postulate a denser CO2-rich atmosphere than at present. Such an atmosphere should have led to the formation of outcrops rich in carbonate minerals, for which evidence has been sparse. Using the Mars Exploration Rover Spirit, we have now identified outcrops rich in magnesium-iron carbonate (16 to 34 weight percent) in the Columbia Hills of Gusev crater. Its composition approximates the average composition of the carbonate globules in martian meteorite ALH 84001. The Gusev carbonate probably precipitated from carbonate-bearing solutions under hydrothermal conditions at near-neutral pH in association with volcanic activity during the Noachian era.

Near-term lander experiments for growing plants on Mars: requirements for information on chemical and physical properties of Mars regolith.

In order to support humans for long-duration missions to Mars, bioregenerative Advanced Life Support (ALS) systems have been proposed that would use higher plants as the primary candidates for photosynthesis. Hydroponic technologies have been suggested as the primary method of plant production in ALS systems, but the use of Mars regolith as a plant growth medium may have several advantages over hydroponic systems. The advantages for using Mars regolith include the likely bioavailability of plant-essential ions, mechanical support for plants, and easy access of the material once on the surface. We propose that plant biology experiments must be included in near-term Mars lander missions in order to begin defining the optimum approach for growing plants on Mars. Second, we discuss a range of soil chemistry and soil physics tests that must be conducted prior to, or in concert with, a plant biology experiment in order to properly interpret the results of plant growth studies in Mars regolith. The recommended chemical tests include measurements on soil pH, electrical conductivity and soluble salts, redox potential, bioavailability of essential plant nutrients, and bioavailability of phytotoxic elements. In addition, a future plant growth experiment should include procedures for determining the buffering and leaching requirements of Mars regolith prior to planting. Soil physical tests useful for plant biology studies in Mars regolith include bulk density, particle size distribution, porosity, water retention, and hydraulic conductivity.