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.

Fatty Acid Preservation in Modern and Relict Hot-Spring Deposits in Iceland, with Implications for Organics Detection on Mars.

Hydrothermal spring deposits host unique microbial ecosystems and have the capacity to preserve microbial communities as biosignatures within siliceous sinter layers. This quality makes terrestrial hot springs appealing natural laboratories to study the preservation of both organic and morphologic biosignatures. The discovery of hydrothermal deposits on Mars has called attention to these hot springs as Mars-analog environments, driving forward the study of biosignature preservation in these settings to help prepare future missions targeting the recovery of biosignatures from martian hot-spring deposits. This study quantifies the fatty acid load in three Icelandic hot-spring deposits ranging from modern and inactive to relict. Samples were collected from both the surface and 2-18 cm in depth to approximate the drilling capabilities of current and upcoming Mars rovers. To determine the preservation potential of organics in siliceous sinter deposits, fatty acid analyses were performed with pyrolysis-gas chromatography-mass spectrometry (GC-MS) utilizing thermochemolysis with tetramethylammonium hydroxide (TMAH). This technique is available on both current and upcoming Mars rovers. Results reveal that fatty acids are often degraded in the subsurface relative to surface samples but are preserved and detectable with the TMAH pyrolysis-GC-MS method. Hot-spring mid-to-distal aprons are often the best texturally and geomorphically definable feature in older, degraded terrestrial sinter systems and are therefore most readily detectable on Mars from orbital images. These findings have implications for the detection of organics in martian hydrothermal systems as they suggest that organics might be detectable on Mars in relatively recent hot-spring deposits, but preservation likely deteriorates over geological timescales. Rovers with thermochemolysis pyrolysis-GC-MS instrumentation may be able to detect fatty acids in hot-spring deposits if the organics are relatively young; therefore, martian landing site and sample selection are of paramount importance in the search for organics on Mars.

Lipid Biomarkers in Ephemeral Acid Salt Lake Mudflat/Sandflat Sediments: Implications for Mars.

Sedimentary strata on Mars often contain a mix of sulfates, iron oxides, chlorides, and phyllosilicates, a mineral assemblage that is unique on Earth to acid brine environments. To help characterize the astrobiological potential of depositional environments with similar minerals present, samples from four naturally occurring acidic salt lakes and adjacent mudflats/sandflats in the vicinity of Norseman, Western Australia, were collected and analyzed. Lipid biomarkers were extracted and quantified, revealing biomarkers from vascular plants alongside trace microbial lipids. The resilience of lipids from dead organic material in these acid saline sediments through the pervasive stages of early diagenesis lends support to the idea that sulfates, in tandem with phyllosilicates and iron oxides, could be a viable target for biomarkers on Mars. To fully understand the astrobiological potential of these depositional environments, additional investigations of organic preservation in ancient acidic saline sedimentary environments are needed.

Recovery of Fatty Acids from Mineralogic Mars Analogs by TMAH Thermochemolysis for the Sample Analysis at Mars Wet Chemistry Experiment on the Curiosity Rover.

The Mars Curiosity rover carries a diverse instrument payload to characterize habitable environments in the sedimentary layers of Aeolis Mons. One of these instruments is Sample Analysis at Mars (SAM), which contains a mass spectrometer that is capable of detecting organic compounds via pyrolysis gas chromatography mass spectrometry (py-GC-MS). To identify polar organic molecules, the SAM instrument carries the thermochemolysis reagent tetramethylammonium hydroxide (TMAH) in methanol (hereafter referred to as TMAH). TMAH can liberate fatty acids bound in macromolecules or chemically bound monomers associated with mineral phases and make these organics detectable via gas chromatography mass spectrometry (GC-MS) by methylation. Fatty acids, a type of carboxylic acid that contains a carboxyl functional group, are of particular interest given their presence in both biotic and abiotic materials. This work represents the first analyses of a suite of Mars-analog samples using the TMAH experiment under select SAM-like conditions. Samples analyzed include iron oxyhydroxides and iron oxyhydroxysulfates, a mixture of iron oxides/oxyhydroxides and clays, iron sulfide, siliceous sinter, carbonates, and shale. The TMAH experiments produced detectable signals under SAM-like pyrolysis conditions when organics were present either at high concentrations or in geologically modern systems. Although only a few analog samples exhibited a high abundance and variety of fatty acid methyl esters (FAMEs), FAMEs were detected in the majority of analog samples tested. When utilized, the TMAH thermochemolysis experiment on SAM could be an opportunity to detect organic molecules bound in macromolecules on Mars. The detection of a FAME profile is of great astrobiological interest, as it could provide information regarding the source of martian organic material detected by SAM.