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In this work, we have analyzed natural samples collected at three hydrothermal areas of Iceland by Raman spectroscopy. The studied high-latitude regions are considered environmentally and mineralogically appropriate Martian analogues since they are rich in weathered basalts that have been altered by hydrothermalism to mineral phases such as silica, clay minerals, sulfates, oxides, and sulfur. The main objective of this work was to assess the relation of the spectroscopic signatures of alteration to hydrothermal processes and biomediation, considering previous studies focused on the detection of lipid biomarkers in the same samples. The recorded Raman spectra, taken with optical parameters similar to the ExoMars 2022 Raman spectrometer, showed structural modifications in all secondary minerals in the form of peak shifts (in the case of sulfur and clay minerals), changes in the relative ratio intensity (in anatase) and/or shape broadening (in sulfates and hematite). These results reveal the suitability of Raman spectroscopy to examine areas rich in water-altered minerals, where a mixture of crystalline and amorphous phases can co-exist. The detection of silica is singularly interesting since, on the one hand, it can imply the past existence of hydrothermal hot springs rich in nutrient and redox gradients and, on the other hand, provides excellent matrix for biosignature preservation. The data can be helpful as an astrobiological database for the forthcoming missions to Mars, where potential upwelling groundwater systems could have altered the mineral phases in a similar way to that observed in this work.

The presence of organic matter in lacustrine mudstone sediments at Gale crater was revealed by the Mars Science Laboratory Curiosity rover, which also identified smectite clay minerals. Analogue experiments on phyllosilicates formed under low temperature aqueous conditons have illustrated that these are excellent reservoirs to host organic compounds against the harsh surface conditions of Mars. Here, we evaluate whether the capacity of smectites to preserve organic compounds can be influenced by a short exposure to different diagenetic fluids. We analyzed the stability of glycine embedded within nontronite samples previously exposed to either acidic or alkaline fluids (hereafter referred to as "treated nontronites") under Mars-like surface conditions. Analyses performed using multiple techniques showed higher photodegradation of glycine in the acid-treated nontronite, triggered by decarboxylation and deamination processes. In constrast, our experiments showed that glycine molecules were preferably incorporated by ion exchange in the interlayer region of the alkali-treated nontronite, conferring them a better protection against the external conditions. Our results demonstrate that smectite previously exposed to fluids with different pH values influences how glycine is adsorbed into their interlayer regions, affecting their potential for preservation of organic compounds under contemporary Mars surface conditions. The research leading to these results is a contribution from the Projects "icyMARS" and "MarsFirstWater", funded by the European Research Council, Starting Grant no. 307496 and Consolidator Grant no. 818602, respectively, to AGF. We acknowledge to S. Galvez-Martinez for help and support during XPS measurements and the technical staff of the Unidad de Tecnicas Geologicas (Universidad Complutense de Madrid) for the XRD measurements. This Project has been partially supported by Unidad de Excelencia "Maria de Maeztu", MDM-2017-0737, Centro de Astrobiologia (INTA-CSIC), OPB is supported by project ESP2017-89053-C2-1-P and EMM by project ESP2017-89053-C2-2-P. Peer review