Oxygen isotope fractionation in the Martian atmosphere induced by CO$_2$ photolysis and O$_3$ formation

Abstract

The enrichment of heavy isotopes of volatile elements in the Martian atmosphere indicates that Mars lost a large portion of its atmosphere through escape to space. Recent atmospheric measurements by ExoMars Trace Gas Orbiter (TGO) have suggested that the vertical profiles of oxygen isotopic compositions are influenced by chemical reactions involving isotopic fractionation. However, their quantitative impacts have not yet been fully evaluated. In this study, we develop a 1D photochemical model that incorporates oxygen isotopic fractionation associated with CO$_2$ photolysis and O$_3$ formation to investigate the vertical profiles of oxygen isotopic compositions. Our calculations show that CO is depleted in heavy oxygen isotopes relative to CO$_2$, reaching $δ^{18}$O $\sim -25$ per mil and $δ^{17}$O $\sim -15$ per mil, primarily due to isotopic fractionation during CO$_2$ photolysis. The vertical profiles of oxygen and carbon isotopic compositions are in good agreement between our model and the TGO measurements. O$_3$ is strongly enriched in $^{18}$O and $^{17}$O, reaching $δ^{18}$O $\sim 100$ per mil and $δ^{17}$O $\sim 50$ per mil as a consequence of the isotopic fractionation during its formation, whereas atomic oxygen is highly depleted in the heavy oxygen isotopes with $δ^{18}$O $\lesssim -100$ per mil and $δ^{17}$O $\lesssim -50$ per mil so as to compensate for their enrichment in O$_3$. These chemical fractionation processes can deplete the heavy oxygen isotopes in species that escape from the upper atmosphere, and thereby enhance the isotopic fractionation associated with oxygen escape to space. Such fractionated isotopic compositions of escaping oxygen may be detectable by the Martian Moons eXploration (MMX) mission.