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Introduction: The identification of perchlorate (ClO4(-)) on Mars has led to the possibility that complete redox couples are available for microbial metabolism in contemporary surface environments. Perchlorate-reducing bacteria (PRB) utilize ClO4(-) and chlorate (ClO3(-)) as terminal electron acceptors due to the high reduction potential. Additionally, ClO4(-) salts have been suggested as a possible source of brines on Mars and spectral evidence indicates that the hydration of ClO4(-) salts in the regolith of Martian is linked to the surface recurring slope lineae (RSL). For these reasons PRB may serve as analog organisms for possible life on Mars. However, there is very little information on the viability of PRB in aqueous environments that contain high levels of perchlorate Microorganisms on or near the surface of Mars, such as in the RSL, would potentially be exposed to high-salinity and high ultraviolet radiation environments. Under these extreme conditions, microorganisms must possess mechanisms for maintaining continued high genome fidelity. To assess possible microbial viability in contemporary Mars analog environments we are investigating the tolerance of two PRB strains in aqueous conditions under high UV-C conditions and high ClO4(-) concentrations.

Biomarkers for life on Earth are an important starting point to guide the search for life elsewhere. However, the search for life beyond Earth should incorporate technologies capable of recognizing an array of potential biomarkers beyond what we see on Earth, in order to minimize the risk of false negatives from life detection missions. With this in mind, charged linear polymers may be a universal signature for life, due to their ability to store information while also inherently reducing the tendency of complex tertiary structure formation that significantly inhibit replication. Thus, these molecules are attractive targets for biosignature detection as potential "self-sustaining chemical signatures." Examples of charged linear polymers, or polyelectrolytes, include deoxyribonucleic acid (DNA) and ribonucleic acid (RNA) as well as synthetic polyelectrolytes that could potentially support life, including threose nucleic acid (TNA) and other xenonucleic acids (XNAs). Nanopore analysis is a novel technology that has been developed for singlemolecule sequencing with exquisite single nucleotide resolution which is also well-suited for analysis of polyelectrolyte molecules. Nanopore analysis has the ability to detect repeating sequences of electrical charges in organic linear polymers, and it is not molecule- specific (i.e. it is not restricted to only DNA or RNA). In this sense, it is a better life detection technique than approaches that are based on specific molecules, such as the polymerase chain reaction (PCR), which requires that the molecule being detected be composed of DNA.

Future directions for investigations and measurements identified in the decadal survey Vision and Voyages for Planetary Science in the Decade 2013-2022 include direct methods to search for extant life. Within the framework a 35-year science vision for future decades extending into the 2020s and beyond, "Ocean Worlds" of the outer Solar System (e.g., Enceladus and Europa), as well as Mars, represent accessible targets that likely provide habitable environments that may support extant life. NASA Ames Research Center (ARC) is currently developing a multi-dimensional approach, led by astrobiology scientists in the ARC Space Sciences Division, technologists in the ARC Exploration Technology Directorate, and small payload engineers in the ARC Mission Design Division, to enable the definitive detection of extant extraterrestrial life in future NASA missions.

The Mars Phoenix Lander's TEGA instrument detected a calcium carbonate phase decomposing at high temperatures (approx.700 C) from the Wicked Witch soil sample [1]. TEGA also detected a lower temperature CO2 release between 400 C and 680 C [1]. Possible explanations given for this lower temperature CO2 release include thermal decomposition of Mg or Fe carbonates, a zeolitictype desorption reaction, or combustion of organic compounds in the soil [2]. The detection of 0.6 wt % soluble perchlorate by the Wet Chemistry Laboratory (WCL) on Phoenix [3] has implications for the possibility of organic molecules in the soil. Ming et al. [4] demonstrated that perchlorates could have oxidized organic compounds to CO2 in TEGA, preventing detection of their characteristic mass fragments. Here, we propose that a perchlorate salt and calcium carbonate present in martian soil reacted to produce the 400 C - 680 C TEGA CO2 release. The parent salts of the perchlorate on Mars are unknown, but geochemical models using WCL data support the possible dominance of Mg-perchlorate salts [5]. Mg(ClO4)2 6H2O is the stable phase at ambient martian conditions [6], and breaks down at lower temperatures than carbonates giving off Cl2 and HCl gas [7,8]. Devlin and Herley [7] report two exotherms at 410-478 C and 473-533 C which correspond to the decomposition of Mg(ClO4)2.

Over the past several decades, elemental sulfur in martian soils and rocks has been detected by a number of missions using X-ray spectroscopy [1-3]. Optical spectroscopy has also provided evidence for widespread sulfates on Mars [4,5]. The ubiquitous presence of sulfur in soils has been interpreted as a widely distributed sulfate mineralogy [6]. However, direct confirmation as to the identity and solubility of the sulfur species in martian soil has never been obtained. One goal of the Wet Chemistry Laboratory (WCL) [7] on board the 2007 Phoenix Mars Lander [8] was to determine soluble sulfate in the martian soil. The WCL received three primary samples. Each sample was added to 25 mL of leaching solution and analysed for solvated ionic species, pH, and conductivity [9,10]. The analysis also showed a discrepancy between charge balance, ionic strength, and conductivity, suggesting unidentified anionic species.

We describe the use of a novel sensor, designed to characterize the reactive nature of the Martian atmosphere, to also characterize the instantaneous abundance of atmospheric H,O. The sensor deposits, in situ, a thin silver film onto a sapphire substrate and monitors oxidation by measuring resistance of the Ag film during both deposition and subsequent oxidation [1,2]. . The evaporation source is placed in the center of a hollow, open-ended tube. On flash heating the source, evaporated metallic silver rapidly reacts with oxidizing gases in the tube, depositing on the tube walls as a resisitive Ag oxide film. Unoxidized silver deposits over the Ag oxides, once the oxidizing gases in the vicinity of the source have been consumed. Since the ends of the tube are open, atmospheric gases in the tube cause a time delay as the evaporated silver initially reacts with the available O2, and H2O; once oxidizing gases in the tube are significantly depleted, a silver film closes the chemiresistor circuit. In principle this operation mode provides a repeatable measure of the variable H2O abundance, since O2, levels are constant in the atmosphere. To explore the utility of the instrument as an H2O sensor, predict its behavior, and identify possible failure modes, we developed a numerical model of the instrument, and exercised it for Mars conditions. The model predicts the behavior of the electrical circuit, the temperature dependence of resistivity for each component, and the resultant Joule heating. The model balances Joule heating against radiation, sensible heat loss to ambient CO2, and, latent heat loss from sublimating Ag. The flux of Ag atoms from the source is tracked continuously. In the gas phase, the number density of Ag, O2, and H2O is calculated, along with their reaction rates on collision. The model suggests that Ag substantially depletes H2O only near the center of the tube. The model supports the hypothesis that the onset of high conductivity between the A u electrodes is a function of the H2O abundance in the ambient gas, but only to a limit; when H2O abundances are buffered at or above 240K (an H2O abundance that would not have occurred on Mars), metallic Ag never deposits in excess of Ago, and the circuit does not close. A significant difference in the Mars simulation is that the Ag source sublimates more quickly, primarily because of differences in sensible heat fluxes from the source. This allows subsequent heating of the W filament used to support the Ag source. Had the originally-designed experimental sequence been carried out on Mars, the filament might have melted, making subsequent investigations impossible.

It has been discovered recently that soils from certain regions of the Chilean Atacama Desert have some characteristics that are similar to the surface materials tested by the Viking Landers. Navarro-Gonzalez et al. demonstrated that the quantity and diversity of heterotrophic bacteria increase as a function of local water availability in the Atacama, and that for some soil samples collected in the driest regions, no culturable bacteria could be isolated. Additionally, Navarro-Gonzalez et al. reported that pyrolysis-GCMS analysis of soils collected from these regions revealed extremely low levels of organic matter. Although the mechanism resulting in the low level of organics in these regions was not established by Navarro-Gonzalez, the condition of organic-depleted, near-sterile soil offers an interesting Earth analog of the martian surface material, as the Viking Gas Exchange (GEx) experiment and Labeled Release (LR) experiment were unable to demonstrate the presence of culturable bacteria, and the Viking pyrolysis- GCMS was unable to detect organic compounds.

The motivation for this work is to perform quantitative site characterizations of soil chemical processes to allow further development and field validation of the Mars Oxidant Instrument (MOI). The MOI is an in situ survey instrument designed to establish the presence of reactive chemical species in the martian soil, dust, or atmosphere, and to provide detailed reaction model system measurements to enable comprehensive Earthbased study. Functioning as a survey instrument, MOI tests the broad range of hypotheses explaining the reactivity of the martian surface material that have been put forth since the Viking experiments. This work is currently being carried out under the NASA ASTEP funded AstroBioLab (Jeffery Bada, PI). A second objective is to use Atacama field and Viking data to perform comparative studies, with the goal of furthering the understanding of the formation mechanisms and properties of martian oxidants.

We describe a chemometric array sensor, the Mars Atmospheric Oxidant Sensor (MAOS) that is designed to measure the oxidation rate of thin films on the martian surface. MAOS will discriminate among leading hypotheses for oxidant production. Additional information is contained in the original extended abstract.

We describe a chemometric array sensor, the Mars Atmospheric Oxidant Sensor (MAOS, pronounced "mouse '') that is designed measure the oxidation rate of thin films on the martian surface. We select films that are sensitive to particular types of oxidants, that represent key elements in the martian soil, or that emulate prebiotic materials. Concern that naturally arising martian oxidants may have destroyed evidence of ancient life on Mars was raised by the Viking mission in the 1970's. The possibility that oxidants may limit the viability of biologica1 habitats is particularly timely in light of recent suggestions of contemporary flowing water on Mars. By controlling the temperature of the films, as well as their exposure to dust and ultraviolet light, MAOS will discriminate among leading hypotheses for oxidant production. MAOS weighs 55 grams, fits in a 6 x 7 x 2 cm envelope, and uses 250 mW power. Much of the enabling technology was developed for the MOx experiment, lost on the Russian Mars '96 mission.

We report on experimental investigations of the photo-induced decomposition of calcium carbonate in both a simulated martian atmosphere and under high vacuum. Additional information is contained in the original extended abstract.

Observations of the Martian planetary boundary layer lead to interpretations that are baffling and contradictory. In this paper, we specifically address the question of whether or not water vapor finds a substantial diurnal reservoir in the Martian regolith. To address this issue, we have measured H2O adsorption kinetics on SWy-1, a Na-rich montmorillonite from Wyoming. The highest-temperature (273 K) data equilibrates rapidly. Data gathered at realistic H2O partial pressures and temperatures appropriate to early morning show two phenomena that preclude a significant role for smectites in diurnally exchanging a large column abundance. First, the equilibration timescale is longer than a sol. Second, the equilibrium abundances are a small fraction of that predicted by earlier adsorption isotherms. The explanation for this phenomenon is that smectite clay actually increases its surface area as a function of adsorptive coverage. At Mars-like conditions, we show that the interlayer sites of smectites are likely to be unavailable.

The adsorptive equilibration of H2O with montomorillonite has been measured. At low temperatures and pressures equilibration can require many hours, effectively preventing smectites at the martian surface from responding to diurnal pressure and temperature variations.

Hydrogen peroxide chemisorbed on titanium dioxide (peroxide-modified titanium dioxide) is investigated as a chemical analog to the putative soil oxidants responsible for the chemical reactivity seen in the Viking biology experiments. When peroxide-modified titanium dioxide (anatase) was exposed to a solution similar to the Viking labeled release (LR) experiment organic medium, CO2 gas was released into the sample cell headspace. Storage of these samples at 10 degrees C for 48 hr prior to exposure to organics resulted in a positive response while storage for 7 days did not. In the Viking LR experiment, storage of the Martian surface samples for 2 sols (approximately 49 hr) resulted in a positive response while storage for 141 sols essentially eliminated the initial rapid release of CO2. Heating the peroxide-modified titanium dioxide to 50 degrees C prior to exposure to organics resulted in a negative response. This is similar to, but not identical to, the Viking samples where heating to approximately 46 degrees C diminished the response by 54-80% and heating to 51.5 apparently eliminated the response. When exposed to water vapor, the peroxide-modified titanium dioxide samples release O2 in a manner similar to the release seen in the Viking gas exchange experiment (GEx). Reactivity is retained upon heating at 50 degrees C for three hours, distinguishing this active agent from the one responsible for the release of CO2 from aqueous organics. The release of CO2 by the peroxide-modified titanium dioxide is attributed to the decomposition of organics by outer-sphere peroxide complexes associated with surface hydroxyl groups, while the release of O2 upon humidification is attributed to more stable inner-sphere peroxide complexes associated with Ti4+ cations. Heating the peroxide-modified titanium dioxide to 145 degrees C inhibited the release of O2, while in the Viking experiments heating to this temperature diminished but did not eliminated the response. Although the thermal stability of the titanium-peroxide complexes in this work is lower than the stability seen in the Viking experiments, it is expected that similar types of complexes will form in titanium containing minerals other than anatase and the stability of these complexes will vary with surface hydroxylation and mineralogy.

The MOx instrument was developed to characterize the reactive nature of the martian soil. The objectives of MOx were: (1) to measure the rate of degradation of organics in the martian environment; (2) to determine if the reactions seen by the Viking biology experiments were caused by a soil oxidant and measure the reactivity of the soil and atmosphere: (3) to monitor the degradation, when exposed to the martian environment, of materials of potential use in future missions; and, finally, (4) to develop technologies and approaches that can be part of future soil analysis instrumentation. The basic approach taken in the MOx instrument was to place a variety of materials composed as thin films in contact with the soil and monitor the physical and chemical changes that result. The optical reflectance of the thin films was the primary sensing-mode. Thin films of organic materials, metals, and semiconductors were prepared. Laboratory simulations demonstrated the response of thin films to active oxidants.

We have measured the adsorption of molecular nitrogen (N2) on palagonite, and modeled the adsorbed nitrogen inventory on the martian regolith. We were motivated by the fact that models of isotopic evolution predict stronger N2 fractionation than reported by Viking. Possible scenarios for reconciling models with the observation include a heavy CO2 atmosphere early in the planet's history, continued outgassing of N2 throughout the history of Mars, or a substantial adsorbed inventory. In this paper we investigate the plausibility of the last explanation. We find that the regolith reservoir of adsorbed N2 is inadequate by itself to buffer the atmospheric isotopic composition, but may play a role depending on the total regolith surface area available.