Influence of mineralogy on the preservation of amino acids under simulated Mars conditions

Abstract

The detection of organic molecules associated with life on Mars is one of the main goals of future life-searching missions such as the ESA-Roscosmos ExoMars and NASA 2020 mission. In this work we studied the preservation of 25 amino acids that were spiked onto the Mars-relevant minerals augite, enstatite, goethite, gypsum, hematite, jarosite, labradorite, montmorillonite, nontronite, olivine and saponite, and on basaltic lava under simulated Mars conditions. Simulations were performed using the Open University Mars Chamber, which mimicked the main aspects of the martian environment, such as temperature, UV radiation and atmospheric pressure. Quantification and enantiomeric separation of the amino acids were performed using gas-chromatography-mass spectrometry (GC–MS). Results show that no amino acids could be detected on the mineral samples spiked with 1 µM amino acid solution (0.1 µmol of amino acid per gram of mineral) subjected to simulation, possibly due to complete degradation of the amino acids and/or low extractability of the amino acids from the minerals. For higher amino acid concentrations, nontronite had the highest preservation rate in the experiments in which 50 µM spiking solution was used (5 µmol/g), while jarosite and gypsum had a higher preservation rate in the experiments in which 25 and 10 µM spiking solutions were used (2.5 and 1 µmol/g), respectively. Overall, the 3 smectite minerals (montmorillonite, saponite, nontronite) and the two sulfates (gypsum, jarosite) preserved the highest amino acid proportions. Our data suggest that clay minerals preserve amino acids due to their high surface areas and small pore sizes, whereas sulfates protect amino acids likely due to their opacity to UV radiation or by partial dissolution and crystallization and trapping of the amino acids. Minerals containing ferrous iron (such as augite, enstatite and basaltic lava) preserved the lowest amount of amino acids, which is explained by iron (II) catalyzed reactions with reactive oxygen species generated under Mars-like conditions. Olivine (forsterite) preserved more amino acids than the other non-clay silicates due to low or absent ferrous iron. Our results show that D- and L-amino acids are degraded at equal rates, and that there is a certain correlation between preservation/degradation of amino acids and their molecular structure: alkyl substitution in the α-carbon seem to contribute towards amino acid stability under UV radiation. These results contribute towards a better selection of sampling sites for the search of biomarkers on future life detection missions on the surface of Mars.