Stability of Atmospheric Redox States of Early Mars Inferred from Time Response of the Regulation of H and O Losses

The ratio of total losses of H and O from the atmosphere is crucial for determining the Martian atmospheric redox state. The H and O escapes are shown to be regulated in a stoichiometric 2:1 ratio in a converged model of present-day Mars over a timescale of ∼105 yr, which is called self-regulation. Self-regulation timescales under different atmospheric conditions on early Mars are not well understood. Here we use a 1D photochemical model to calculate the timescales of self-regulation for denser CO2 atmospheres with various surface temperatures as benchmark cases for early Mars. Self-regulation is driven by variations in the amount of O2 or CO in the atmosphere, depending on the atmospheric redox state. Self-regulation timescales are likely to be controlled by the net redox balance. A 1 bar CO2 atmosphere with a surface temperature of 240 K has a self-regulation timescale of a few million years. Denser atmospheres of early Mars have a longer regulation timescale and are less redox-stable than the atmosphere of present-day Mars. Obliquity variations cause atmospheric CO2 fluctuations, producing a difference in the self-regulation timescale between high and low obliquity. Because an increase in CO2 suppresses H escape, the net effect of the obliquity cycle could have driven the atmospheric redox states to be more reducing. Our results also suggest the possibility of a CO-dominated atmosphere of 10-100 mbars at 3 Ga. The redox state of ancient Mars might have fluctuated more easily than that of the present.