Mars atmospheric loss and isotopic fractionation by pick-up-ion sputtering and photochemical escape

We examine the effects of loss of constituents of the Martian atmosphere due to sputtering by solar-wind pick-up ions and photochemical escape during the last 3.8 billion years. Sputtering is capable of efficiently removing species from the upper atmosphere to space, including the light noble gases; nitrogen and oxygen are removed by both sputtering ad photochemical processes. Due to diffusive separation (by mass) above the homopause, removal from the top of the atmosphere will fractionate the isotopes of each species, with the lighter isotope being preferentially lost. This allows current measurements of the isotopic ratios to be used as a measure of the atmospheric evolution as integrated over geologic time. For carbon and oxygen, isotopic fractionation is buffered by exchange of atmospheric species with non-atmospheric reservoirs of CO2 and H2O. This allows us to determine the size of the non-atmospheric reservoirs which are capable of mixing with the atmosphere; these reservoirs can be CO2 absorbed in the regolith and/or H2O in the polar ice caps. Such an exchangeable reservoir is required in order to keep the fractionation of the atmospheric gases as low as is observed.