The D/H ratio in water on Mars, Rwater, is 4–6× the Earth ratio, signifying past water loss to space. Recently, measurements have revealed high values of the D/H ratio in hydrogen, Ratomic, in the thermosphere during southern summer. Here, we use a photochemical model to explore the potential drivers of Ratomic, testing three: thermospheric temperatures, excess mesospheric water, and changing insolation. We find that Ratomic can achieve values between 15× the Earth ratio (due to water) and 25× the Earth ratio (due to temperature). The effects arise because H escape is diffusion-limited, while D escape is energy-limited. Our results underscore how Ratomic reflects mesospheric dynamics, and the need for concurrent measurements of mesospheric water, thermospheric temperatures, and Ratomic to understand seasonal changes in the martian water cycle and atmospheric loss.

Although deuterium (D) on Mars has received substantial attention, the deuterated ionosphere remains relatively unstudied. This means that we also know very little about non-thermal D escape from Mars, since it is primarily driven by excess energy imparted to atoms produced in ion-neutral reactions. Most D escape from Mars is expected to be non-thermal, highlighting a gap in our understanding of water loss from Mars. In this work, we set out to fill this knowledge gap. To accomplish our goals, we use an upgraded 1D photochemical model that fully couples ions and neutrals and does not assume photochemical equilibrium. To our knowledge, such a model has not been applied to Mars previously. We model the atmosphere during solar minimum, mean, and maximum, and find that the deuterated ionosphere behaves similarly to the H-bearing ionosphere, but that non-thermal escape on the order of 8000-9000 cm-2s-1 dominates atomic D loss under all solar conditions. The total fractionation factor, f, is 0.04–0.07, and integrated water loss is 147–158 m GEL. This is still less than geomorphological estimates. Deuterated ions at Mars are likely difficult to measure with current techniques due to low densities and mass degeneracies with more abundant H ions. Future missions wishing to measure the deuterated ionosphere in situ will need to develop innovative techniques to do so.

Much of the water that once flowed on the surface of Mars was lost to space long ago, and the total amount lost remains unknown. Clues to the amount lost can be found by studying hydrogen (H) and its isotope deuterium (D), both of which are produced when atmospheric water molecules H$_2$O and HDO dissociate. The freed H and D atoms then escape to space at different rates due to their different masses, leaving an enhanced D/H ratio. The rate of change of D/H is referred to as the fractionation factor $f$. Both the D/H ratio and $f$ are necessary to estimate water loss; thus, if we can constrain the range of $f$, we will be able to estimate water loss more accurately. In this study, we use a 1D photochemical model of the Martian atmosphere to determine how $f$ depends on assumed temperature and water vapor profiles. We find that for most Martian atmospheric conditions, $f$ varies between $10^{-1}$ and $10^{-5}$; for the standard Martian atmosphere, $f=0.002$ for thermal escape processes, and $f\approxeq0.06$ when both thermal and non-thermal escape are considered. Using these results, we estimate that Mars has lost at minimum 66-123 m GEL of water. Our results demonstrate that the value of $f$ is almost completely controlled by the amount of non-thermal escape of D, and that photochemical modeling studies that include fractionation must thus model both neutral and ion processes throughout the atmosphere.

Lower atmosphere variations in the martian water vapour and hydrogen abundance during the Mars Year (MY) 34 C storm from LS=326.1◦-333.5◦ and their associated effect on hydrogen escape are investigated using a multi-spacecraft assimilation of atmospheric retrievals into a Martian global circulation model. Elevation of the hygropause and associated increase in middle atmosphere hydrogen at the peak of the MY 34 C storm led to a hydrogen escape rate of around 1.4×109 cm−2s−1 , meaning the MY 34 C storm enhanced water loss rates on Mars to levels observed during global-scale dust storms. The water loss rate during the MY 34 C storm (a loss of 15% of the total annual water loss during only 5% of the year) was three times stronger than the weak MY 30 C storm assimilation, demonstrating that interannual variations in C storm strength must be considered when calculating the integrated loss of water on Mars.