Adsorption of methane and CO₂ onto olivine surfaces in Martian dust conditions

Methane has been detected on all planets of our Solar System, and most of the larger moons, as well as in dwarf-planets like Pluto and Eric. The presence of this molecule in rocky planets is very interesting because its presence in the Earth's atmosphere is mainly related to biotic processes. Space instrumentation in orbiters around Mars has detected olivine on the Martian soil and dust. On the other hand the measurements of methane from the Curiosity rover report detection of background levels of atmospheric methane with abundance that is lower than model estimates of ultraviolet degradation of accreted interplanetary dust particles or carbonaceous chondrite material. Additionally, elevated levels of methane about this background have been observed implying that Mars is episodically producing methane from an additional unknown source, making the reasons of these temporal fluctuations of methane a hot topic in planetary research. The goal of this study is to investigate at atomic level the interactions during the adsorption processes of methane and other Mars atmospheric species (CO₂, H₂O) on forsterite surfaces, through electronic structure calculations based on the Density Functional Theory (DFT). We propose two models to simulate the interaction of adsorbates with the surface of dust mineral, such as binary mixtures (5CH₄+5H₂O/5CH₄+5CO₂) and as a semi-clathrate adsorption. We have obtained interesting results of the adsorption process in the mixture 5CH₄+5CO₂. Associative and dissociative adsorptions were observed for water and CO₂ molecules. The methane molecules were only trapped and held by water or CO₂ molecules. In the dipolar surface, the adsorption of CO₂ molecules produced new species: one CO from a CO₂ dissociation, and, two CO₂ molecules chemisorbed to mineral surface forming in one case a carbonate group. Our results suggest that CO₂ has a strong interaction with the mineral surface when methane is present. These results could be confirmed after the analysis of the data from the upcoming remote and in-situ observations on Mars, as those to be performed by instruments on the ESA's ExoMars Trace Gas Orbiter and ExoMars rover.