Strong depletion of ¹³C in CO induced by photolysis of CO₂ in the Martian atmosphere calculated by a photochemical model

The isotopic signature of atmospheric carbon offers a unique tracer for the history of the Martian atmosphere and the origin of organic matter on Mars. Photolysis of CO$_{2}$ is known to induce strong isotopic fractionation of carbon between CO$_{2}$ and CO. However, its effect on the carbon isotopic compositions in the Martian atmosphere remains uncertain. Here we develop a 1-D photochemical model considering isotopic fractionation via photolysis of CO$_{2}$ to estimate the vertical profiles of the carbon isotopic compositions of CO and CO$_{2}$ in the Martian atmosphere. We find that CO is depleted in $^{13}$C compared with CO$_{2}$ at each altitude due to the fractionation via CO$_{2}$ photolysis: the minimum value of $\delta ^{13}$C in CO is about $-170$ per mil under the standard eddy diffusion setting. This result supports the hypothesis that fractionated atmospheric CO is responsible for the production of the $^{13}$C-depleted organic carbon in Martian sediments detected by Curiosity Rover through the conversion of CO into organic materials and their deposition on the surface. The photolysis and transport-induced fractionation of CO we report here leads to a $\sim 15$ % decrease in the amount of inferred atmospheric loss when combined with the present-day fractionation of the atmosphere and previous studies of carbon escape to space. The fractionated isotopic composition of CO in the Martian atmosphere may be observed by ExoMars Trace Gas Orbiter (TGO) and ground-based telescopes, and escaping ion species produced by the fractionated carbon-bearing species may be detected by Martian Moons eXploration (MMX) in the future.