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Mars today has no active volcanism and its atmosphere is oxidizing, dominated by the photochemistry of CO2 and H2O. Using a one-dimensional photochemical model, we consider whether plausible volcanic gas fluxes could have switched the redox-state of the past martian atmosphere to reducing conditions. In our model, the total quantity and proportions of volcanic gases depend on the water content, outgassing pressure, and oxygen fugacity of the source melt. We find that with reasonable melt parameters the past martian atmosphere (~3.5 Gyr to present) could have easily reached reducing and anoxic conditions with modest levels of volcanism, >0.14 km^3/yr, well within the range of prior estimates. Counter-intuitively we also find that more reducing melts with lower oxygen fugacity require greater amounts of volcanism to switch a paleo-atmosphere from oxidizing to reducing. The reason is that sulfur is more stable in such melts and lower absolute fluxes of sulfur-bearing gases more than compensate for increases in the proportions of H2 and CO. These results imply that ancient Mars should have experienced periods with anoxic and reducing atmospheres even through the mid-Amazonian whenever volcanic outgassing was sustained at sufficient levels. Reducing anoxic conditions are potentially conducive to the synthesis of prebiotic organic compounds, such as amino acids, and are therefore relevant to the possibility of life on Mars. Also, anoxic reducing conditions should have influenced the type of minerals that were formed on the surface or deposited from the atmosphere such as elemental polysulfur (S8) as a signature of past reducing atmospheres. Finally, our models allow us to estimate the amount of volcanically sourced atmospheric sulfate deposited over Mars' history, approximately 10^6 to 10^9 Tmol, with a spread depending on assumed outgassing rate history and magmatic source conditions., Comment: 6 Figures, 1 Table, 3 Appendices

Whether extant life exists in the martian subsurface is an open question. High concentrations of photochemically produced CO and H2 in the otherwise oxidizing martian atmosphere represent untapped sources of biologically useful free energy. These out-of-equilibrium species diffuse into the regolith, so subsurface microbes could use them as a source of energy and carbon. Indeed, CO oxidation and methanogenesis are relatively simple and evolutionarily ancient metabolisms on Earth. Consequently, assuming CO- or H2- consuming metabolisms would evolve on Mars, the persistence of CO and H2 in the martian atmosphere set limits on subsurface metabolic activity. Here, we constrain such maximum subsurface metabolic activity on Mars using a 1-D photochemical model with a hypothetical global biological sink on atmospheric CO and H2. We increase the biological sink until the model atmospheric composition diverges from observed abundances. We find maximum biological downward subsurface sinks of 1.5e8 molecules/cm^2/s for CO and 1.9e8 molecules/cm^2/s for H2. These covert to a maximum metabolizing biomass of <10^27 cells or <2e11 kg, equivalent to <1e-4 to 1e-5 of Earth's biomass, depending on the terrestrial estimate. Diffusion calculations suggest this upper biomass limit applies to the top few kilometers of the martian crust in communication with the atmosphere at low to mid latitudes. This biomass limit is more robust than previous estimates because we test multiple possible chemoautotrophic ecosystems over a broad parameter space of tunable model variables using an updated photochemical model with precise atmospheric concentrations and uncertainties from Curiosity. Our results of sparse or absent life in the martian subsurface also demonstrate how the atmospheric redox pairs of CO-O2 and H2-O2 may constitute antibiosignatures, which may be relevant to excluding life on exoplanets., Comment: 30 pages, 4 figures, 3 tables. Accepted for publication in Astrobiology