Nitrogen Fixation at Early Mars

The Mars Science Laboratory (MSL) recently discovered nitrates near Gale Crater (eg., Stern et al., 2015; Sutter et al., 2017). One possible mechanism for ancient nitrate deposition at Mars is through HNOx formation and rain-out in the atmosphere, for which lightning-induced NO is likely the fundamental source. This study investigates nitrogen fixation in early Mars’ atmosphere, with implications for early Mars’ habitability. We consider a 1 bar atmosphere of background composition CO₂ with abundances of N₂, H₂, and CH₄ varied from 1-10% to explore a swath of potential early Mars climates. We derive lightning-induced thermochemical equilibrium fluxes of NO and HCN by coupling the lightning-rate parametrization of Romps et al. (2014) with Chemical Equilibrium with Applications, and we use a Geant4 simulation platform to estimate the effect of solar energetic particle (SEP) events. These fluxes are used as input into KINETICS, the Caltech/JPL coupled photochemistry and transport code, which models the chemistry of 50 species linked by 495 reactions to derive rain-out fluxes of HNOx and HCN. We compute equilibrium concentrations of cyanide and nitrate in a putative northern ocean at early Mars, assuming hydrothermal vent circulation and photoreduction act as the dominant loss mechanisms. We find oceanic concentrations of ~0.1-3 nM nitrate and ~0.1-10 μM cyanide. HCN is critical for protein synthesis at concentrations > 0.01 M (eg., Holm and Neubeck, 2009), and our result is astrobiologically relevant if secondary local concentration mechanisms occurred. Nitrates may act as high potential electron acceptors for early metabolisms, though the minimum concentration required is unknown. Our work derives concentrations that will be useful for future laboratory studies to investigate the habitability atearly Mars. Importantly, the aqueous nitrate concentrations correspond to surface nitrate precipitates of ~1–8×10^-4 weight percent that may have formed after the evaporation of surface waters, and these values roughly agree with the lower boundary of recent MSL measurements.