Variable and Large Losses of Diagnostic Biomarkers After Simulated Cosmic Radiation Exposure in Clay- and Carbonate-Rich Mars Analog Samples.

Mars has been exposed to ionizing radiation for several billion years, and as part of the search for life on the Red Planet, it is crucial to understand the impact of radiation on biosignature preservation. Several NASA and ESA missions are looking for evidence of ancient life in samples collected at depths shallow enough that they have been impacted by galactic cosmic rays (GCRs). In this study, we exposed a diverse set of Mars analog samples to 0.9 Megagray (MGy) of gamma radiation to mimic 15 million years of exposure on the Martian surface. We measured no significant impact of GCRs on the total organic carbon (TOC) and bulk stable C isotopes in samples with initial TOC concentration > 0.1 wt. %; however, diagnostic molecular biosignatures presented a wide range of degradation that didn't correlate to factors like mineralogy, TOC, water content, and surface area. Exposure dating suggests that the surface of Gale crater has been irradiated at more than five times our dose, yet using this relatively low dose and "best-case scenario" geologically recalcitrant biomarkers, large and variable losses were nevertheless evident. Our results empasize the importance of selecting sampling sites at depth or recently exposed at the Martian surface.

Raman and UVN+LWIR LIBS detection system for in-situ surface chemical identification.

Laser Induced Breakdown Spectroscopy (LIBS) in the Ultra Violet/Visible/Near-IR (UVN) spectral range is a powerful analytical tool that facilitates the interpretation of Raman spectroscopic data by providing additional details in elemental chemistry. To acquire the complete information of molecular vibrations for more accurate and precise chemical bonding and structural analysis, an ideal in situ optical sensing facility should be able to rapidly probe the broad vibrational dipole and polarizability responses of molecules by acquiring both Raman scattering and mid-IR emission spectroscopic signatures. Recently, the research team at Brimrose has developed a novel optical technology, Long-Wave IR (LWIR) LIBS. Critical experimental approaches were made to capture the infrared molecular emission signatures from vibrationally excited intact samples excited by laser-induced plasma in a LIBS event. LWIR LIBS is the only fieldable mid-IR emission spectroscopic technique to-date that that offers the same instrumental and analytical advantages of both UVN LIBS and Raman spectroscopy in in-situ stand-off field applications and can perform rapid and comprehensive molecular structure analysis without any sample-preparation.•A single excitation laser pulse is used to trigger both UVN and LWIR spectrometers simultaneously.•Time-resolved UVN-LWIR LIBS measurements showed the evolution of both atomic and molecular signature emissions of target compounds in the laser-induced plasma.•The technique was applied to the characterization of mineral and organic compounds in planetary analog samples.

Spectroscopic characterization of samples from different environments in a Volcano-Glacial region in Iceland: Implications for in situ planetary exploration.

Raman spectroscopy and laser induced breakdown spectroscopy (LIBS) are complementary techniques that together can provide a comprehensive characterization of geologic environments. For landed missions with constrained access to target materials on other planetary bodies, discerning signatures of life and habitability can be daunting, particularly where the preservation of organic compounds that contain the building blocks of life is limited. The main challenge facing any spectroscopy measurements of natural samples is the complicated spectra that often contain signatures for multiple components, particularly in rocks that are composed of several minerals with surfaces colonized by microbes. The goal of this study was to use the combination of Raman spectroscopy and LIBS to discern different environmental regimes based on the identification of minerals and biomolecules in rocks and sediments. Iceland is a terrestrial volcano-glacial location that offers a range of planetary analog environments, including volcanically active regions, extensive lava fields, geothermal springs, and large swaths of ice-covered terrain that are relevant to both rocky and icy planetary bodies. We combined portable VIS (532 nm) and NIR (785 nm) Raman spectroscopy, VIS micro-Raman spectroscopic mapping, and UV/VIS/NIR (200 - 1000 nm) and Mid-IR (5.6 - 10 µm, 1785 - 1000 cm-1) laser induced breakdown spectroscopy (LIBS) to characterize the mineral assemblages, hydrated components, and biomolecules in rock and sediment samples collected from three main sites in the volcanically active Kverkfjöll-Vatnajökull region of Iceland: basalt and basalt-hosted carbonate rind from Hveragil geothermal stream, volcanic sediments from the base of Vatnajökull glacier at Kverkfjöll, and lava from the nearby Holuhraun lava field. With our combination of techniques, we were able to identify major mineral polytypes typical for each sample set, as well as a large diversity of biomolecules typical for lichen communities across all samples. The anatase we observed using micro-Raman spectroscopic mapping of the lava compared with the volcanic sediment suggested different formation pathways: lava anatase formed authigenically, sediment anatase could have formed in association with microbial weathering. Mn-oxide, only detected in the carbonate samples, seems to have two possible formation pathways, either by fluvial or microbial weathering or both. Even with our ability to detect a wide diversity of biomolecules and minerals in all of the samples, there was not enough variation between each set to distinguish different environments based on the limited measurements done for this study.

Deciphering Biosignatures in Planetary Contexts.

Microbial life permeates Earth's critical zone and has likely inhabited nearly all our planet's surface and near subsurface since before the beginning of the sedimentary rock record. Given the vast time that Earth has been teeming with life, do astrobiologists truly understand what geological features untouched by biological processes would look like? In the search for extraterrestrial life in the Universe, it is critical to determine what constitutes a biosignature across multiple scales, and how this compares with "abiosignatures" formed by nonliving processes. Developing standards for abiotic and biotic characteristics would provide quantitative metrics for comparison across different data types and observational time frames. The evidence for life detection falls into three categories of biosignatures: (1) substances, such as elemental abundances, isotopes, molecules, allotropes, enantiomers, minerals, and their associated properties; (2) objects that are physical features such as mats, fossils including trace-fossils and microbialites (stromatolites), and concretions; and (3) patterns, such as physical three-dimensional or conceptual n-dimensional relationships of physical or chemical phenomena, including patterns of intermolecular abundances of organic homologues, and patterns of stable isotopic abundances between and within compounds. Five key challenges that warrant future exploration by the astrobiology community include the following: (1) examining phenomena at the "right" spatial scales because biosignatures may elude us if not examined with the appropriate instrumentation or modeling approach at that specific scale; (2) identifying the precise context across multiple spatial and temporal scales to understand how tangible biosignatures may or may not be preserved; (3) increasing capability to mine big data sets to reveal relationships, for example, how Earth's mineral diversity may have evolved in conjunction with life; (4) leveraging cyberinfrastructure for data management of biosignature types, characteristics, and classifications; and (5) using three-dimensional to n-D representations of biotic and abiotic models overlain on multiple overlapping spatial and temporal relationships to provide new insights.