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On Earth, the circulation of Fe-rich fluids in hydrothermal environments leads to characteristic iron mineral deposits, reflecting the pH and redox chemical conditions of the hydrothermal system, and is often associated with chemotroph microorganisms capable of deriving energy from chemical gradients. On Mars, iron-rich hydrothermal sites are considered to be potentially important astrobiological targets for searching evidence of life during exploration missions, such as the Mars 2020 and the ExoMars 2022 missions. In this study, an extinct hydrothermal chimney from the Jaroso hydrothermal system (SE Spain), considered an interesting geodynamic and mineralogical terrestrial analog for Mars, was analyzed using Raman spectroscopy, X-ray diffraction, and scanning electron microscopy coupled with energy dispersive X-ray spectroscopy. The sample consists of a fossil vent in a Miocene shallow-marine sedimentary deposit composed of a marl substrate, an iron-rich chimney pipe, and a central space filled with backfilling deposits and vent condensates. The iron crust is particularly striking due to the combined presence of molecular and morphological indications of a microbial colonization, including mineral microstructures ( e.g., stalks, filaments), iron oxyhydroxide phases (altered goethite, ferrihydrite), and organic signatures (carotenoids, organopolymers). The clear identification of pigments by resonance Raman spectroscopy and the preservation of organics in association with iron oxyhydroxides by Raman microimaging demonstrate that the iron crust was indeed colonized by microbial communities. These analyses confirm that Raman spectroscopy is a powerful tool for documenting the habitability of such historical hydrothermal environments. Finally, based on the results obtained, we propose that the ancient iron-rich hydrothermal pipes should be recognized as singular terrestrial Mars analog specimens to support the preparatory work for robotic in situ exploration missions to Mars, as well as during the subsequent interpretation of data returned by those missions.

In 2020, the ESA ExoMars and NASA Mars 2020 missions will be launched to Mars to search for evidence of past and present life. In preparation for these missions, terrestrial analog samples of rock formations on Mars are studied in detail in order to optimize the scientific information that the analytical instrumentation will return. Desert varnishes are thin mineral coatings found on rocks in arid and semi-arid environments on Earth that are recognized as analog samples. During the formation of desert varnishes (which takes many hundreds of years), organic matter is incorporated, and microorganisms may also play an active role in the formation process. During this study, four complementary analytical techniques proposed for Mars missions (X-ray diffraction [XRD], Raman spectroscopy, elemental analysis, and pyrolysis-gas chromatography-mass spectrometry [Py-GC-MS]) were used to interrogate samples of desert varnish and describe their capacity to sustain life under extreme scenarios. For the first time, both the geochemistry and the organic compounds associated with desert varnish are described with the use of identical sets of samples. XRD and Raman spectroscopy measurements were used to nondestructively interrogate the mineralogy of the samples. In addition, the use of Raman spectroscopy instruments enabled the detection of β-carotene, a highly Raman-active biomarker. The content and the nature of the organic material in the samples were further investigated with elemental analysis and methylated Py-GC-MS, and a bacterial origin was determined to be likely. In the context of planetary exploration, we describe the habitable nature of desert varnish based on the biogeochemical composition of the samples. Possible interference of the geological substrate on the detectability of pyrolysis products is also suggested. Key Words: Desert varnish-Habitability-Raman spectroscopy-Py-GC-MS-XRD-ExoMars-Planetary science. Astrobiology 17, 1123-1137.

Raman spectrometers will be utilized on two Mars rover missions, ExoMars and Mars 2020, in the near future, to search for evidence of life and habitable geological niches on Mars. Carotenoid pigments are recognized target biomarkers, and as they are highly active in Raman spectroscopy, they can be readily used to characterize the capabilities of space representative instrumentation. As part of the preparatory work being performed for the ExoMars mission, a gypsum crust colonized by microorganisms was interrogated with commercial portable Raman instruments and a flight representative Raman laser spectrometer. Four separate layers, each exhibiting different coloration resulting from specific halophilic microorganism activities within the gypsum crust, were studied by using two excitation wavelengths: 532 and 785 nm. Raman or fluorescence data were readily obtained during the present study. Gypsum, the main constituent of the crust, was detected with both excitation wavelengths, while the resonance Raman signal associated with carotenoid pigments was only detected with a 532 nm excitation wavelength. The fluorescence originating from bacteriochlorophyll a was found to overwhelm the Raman signal for the layer colonized by sulfur bacteria when interrogated with a 785 nm excitation wavelength. Finally, it was demonstrated that portable instruments and the prototype were capable of detecting a statistically significant difference in band positions of carotenoid signals between the sample layers. Key Words: Gypsum-Raman spectrometers-Carotenoids-ExoMars-Mars exploration-Band position shift. Astrobiology 17, 351-362.

Desert varnishes are thin, dark mineral coatings found on some rocks in arid or semi-arid environments on Earth. Microorganisms may play an active role in their formation, which takes many hundreds of years. Their mineral matrix may facilitate the preservation of organic matter and is therefore of great relevance to martian exploration. Miniaturized Raman spectrometers (which allow nondestructive analysis of the molecular composition of a specimen) will equip rovers in forthcoming planetary exploration missions. In that context, and for the first time, portable Raman spectrometers operating in the green visible (532 nm as currently baselined for flight) and in the near-infrared (785 nm) were used in this study to investigate the composition (and substrate) of several samples of desert varnish. Rock samples that were suspected (and later confirmed) to be coated with desert varnish were recovered from two sites in the Mojave Desert, USA. The portable spectrometers were operated in flight-representative acquisition modes to identify the key molecular components of the varnish. The results demonstrate that the coatings typically comprise silicate minerals such as quartz, plagioclase feldspars, clays, ferric oxides, and hydroxides and that successful characterization of the samples can be achieved by using flightlike portable spectrometers for both the 532 and 785 nm excitation sources. In the context of searching for spectral signatures and identifying molecules that indicate the presence of extant and/or extinct life, we also report the detection of β-carotene in some of the samples. Analysis complications caused by the presence of rare earth element photoluminescence (which overlaps with and overwhelms the organic Raman signal when a 785 nm laser is employed) are also discussed.

Knowledge and understanding of the martian environment has advanced greatly over the past two decades, beginning with NASA's return to the surface of Mars with the Pathfinder mission and its rover Sojourner in 1997 and continuing today with data being returned by the Curiosity rover. Reduced carbon, however, is yet to be detected on the martian surface, despite its abundance in meteorites originating from the planet. If carbon is detected on Mars, it could be a remnant of extinct life, although an abiotic source is much more likely. If the latter is the case, environmental carbonaceous material would still provide a source of carbon that could be utilized by microbial life for biochemical synthesis and could therefore act as a marker for potential habitats, indicating regions that should be investigated further. For this reason, the detection and characterization of reduced or organic carbon is a top priority for both the ESA/Roscosmos ExoMars rover, currently due for launch in 2018, and for NASA's Mars 2020 mission. Here, we present a Raman spectroscopic study of Archean chert Mars analog samples from the Pilbara Craton, Western Australia. Raman spectra were acquired with a flight-representative 532 nm instrument and a 785 nm instrument with similar operating parameters. Reduced carbon was successfully detected with both instruments; however, its Raman bands were detected more readily with 785 nm excitation, and the corresponding spectra exhibited superior signal-to-noise ratios and reduced background levels.

A novel miniaturized Raman spectrometer is scheduled to fly as part of the analytical instrumentation package on an ESA remote robotic lander in the ESA/Roscosmos ExoMars mission to search for evidence for extant or extinct life on Mars in 2018. The Raman spectrometer will be part of the first-pass analytical stage of the sampling procedure, following detailed surface examination by the PanCam scanning camera unit on the ExoMars rover vehicle. The requirements of the analytical protocol are stringent and critical; this study represents a laboratory blind interrogation of specimens that form a list of materials that are of relevance to martian exploration and at this stage simulates a test of current laboratory instrumentation to highlight the Raman technique strengths and possible weaknesses that may be encountered in practice on the martian surface and from which future studies could be formulated. In this preliminary exercise, some 10 samples that are considered terrestrial representatives of the mineralogy and possible biogeologically modified structures that may be identified on Mars have been examined with Raman spectroscopy, and conclusions have been drawn about the viability of the unambiguous spectral identification of biomolecular life signatures. It is concluded that the Raman spectroscopic technique does indeed demonstrate the capability to identify biomolecular signatures and the mineralogy in real-world terrestrial samples with a very high degree of success without any preconception being made about their origin and classification.