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International audience; The Mars Organic Molecule Analyzer (MOMA) and Sample Analysis at Mars (SAM) instruments onboard the Exomars 2022 and Mars Science Laboratory rovers, respectively, are capable of organic matter detection and differentiating potentially biogenic from abiotic organics in martian samples. To identify organics, both these instruments utilize pyrolysis–gas chromatography coupled to mass spectrometry, and the thermochemolysis agent tetramethylammonium hydroxide (TMAH) is also used to increase organic volatility. However, the reactivity and efficiency of TMAH thermochemolysis are affected by the presence of calcium perchlorate on the martian surface. In this study, we determined the products of TMAH pyrolysis in the presence and absence of calcium perchlorate at different heating rates (flash pyrolysis and SAM-like ramp pyrolysis with a 35°C·min−1 heating rate). The decomposition mechanism of TMAH pyrolysis in the presence of calcium perchlorate was studied by using stepped pyrolysis. Moreover, the effect of calcium perchlorate (at Mars-relevant concentrations) on the recovery rate of fatty acids with TMAH thermochemolysis was studied. Results demonstrate that flash pyrolysis yields more diversity and greater abundances of TMAH thermochemolysis products than does the SAM-like ramp pyrolysis method. There is no obvious effect of calcium perchlorate on TMAH degradation when the [ClO4−] is lower than 10 weight percent (wt %). Most importantly, the presence of calcium perchlorate does not significantly impact the recovery rate of fatty acids with TMAH thermochemolysis under laboratory conditions, which is promising for the detection of fatty acids via TMAH thermochemolysis with the SAM and MOMA instruments on 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.

For the past fifty years of space exploration, mass spectrometry has provided unique chemical and physical insights on the characteristics of other planetary bodies in the Solar System. A variety of mass spectrometer types, including magnetic sector, quadrupole, time-of-flight, and ion trap, have and will continue to deepen our understanding of the formation and evolution of exploration targets like the surfaces and atmospheres of planets and their moons. An important impetus for the continuing exploration of Mars, Europa, Enceladus, Titan, and Venus involves assessing the habitability of solar system bodies and, ultimately, the search for life—a monumental effort that can be advanced by mass spectrometry. Modern flight-capable mass spectrometers, in combination with various sample processing, separation, and ionization techniques enable sensitive detection of chemical biosignatures. While our canonical knowledge of biosignatures is rooted in Terran-based examples, agnostic approaches in astrobiology can cast a wider net, to search for signs of life that may not be based on Terran-like biochemistry. Here, we delve into the search for extraterrestrial chemical and morphological biosignatures and examine several possible approaches to agnostic life detection using mass spectrometry. We discuss how future missions can help ensure that our search strategies are inclusive of unfamiliar life forms.

"Multi-column gas chromatography analysis of chlorohydrocarbons 1with the SAM experiment onboard NASA’s Mars Curiosity rover" est le titre provisoire de la publication.; International audience; The Sample Analysis at Mars (SAM) instrument is a gas chromatograph-mass spectrometer onboard the NASA Curiosity rover, currently operating on the surface of Mars. Organic compounds are of major importance with regard to questions of habitability and the potential presence of life on Mars, and one of the mission’s main objectives is to analyze the organic content of soil and rock samples. In SAM’s first chromatographic measurements, however, unexpected chlorine-bearing organic molecules were detected. These molecules have different origins but the presence of perchlorates and chlorates detected at the surface of Mars suggests that reactivity between organic molecules and thermal decomposition products from oxychlorines is one of the major sources of the chlorinated organic molecules. Here we perform a comprehensive and systematic study of the separation of volatile chlorohydrocarbons with the chromatographic columns used in the SAM instrument. Despite the constrained operating conditions of the flight instrument, we demonstrate that SAM’s capillary chromatographic columns allow for effective separation and identification of a wide range of chlorine-bearing species. We also show that instrumental limitations prevent the detection of certain molecules, obscuring our ability to make definitive conclusions about the origin of these organic materials.

This paper provides an overview of the Curiosity rover's exploration at Vera Rubin ridge and summarizes the science results. Vera Rubin ridge (VRR) is a distinct geomorphic feature on lower Aeolis Mons (informally known as Mt. Sharp) that was identified in orbital data based on its distinct texture, topographic expression, and association with a hematite spectral signature. Curiosity conducted extensive remote sensing observations, acquired data on dozens of contact science targets, and drilled three outcrop samples from the ridge, as well as one outcrop sample immediately below the ridge. Our observations indicate that strata composing VRR were deposited in a predominantly lacustrine setting and are part of the Murray formation. The rocks within the ridge are chemically in family with underlying Murray formation strata. Red hematite is dispersed throughout much of the VRR bedrock, and this is the source of the orbital spectral detection. Gray hematite is also present in isolated, gray‐colored patches concentrated towards the upper elevations of VRR, and these gray patches also contain small, dark Fe‐rich nodules. We propose that VRR formed when diagenetic event(s) preferentially hardened rocks, which were subsequently eroded into a ridge by wind. Diagenesis also led to enhanced crystallization and/or cementation that deepened the ferric‐related spectral absorptions on the ridge, which helped make them readily distinguishable from orbit. Results add to existing evidence of protracted aqueous environments at Gale crater and give new insight into how diagenesis shaped Mars’ rock record.

International audience; Most of the organics detected on Mars so far are aliphatic and aromatic organo‐chlorine compounds. The smallest were first identified by the thermal treatment of the solid samples by Viking in 1976, although at the time, they were attributed to contamination. Since 2012, a larger variety of structures have been identified by the Sample Analysis at Mars (SAM) experiment aboard the Curiosity rover. Evidence suggests that the chlorohydrocarbons formed during pyrolysis of sedimentary materials. Laboratory experiments show that heating of samples containing oxychlorines, such as chlorates (ClO3‐) and perchlorates (ClO4‐), along with organic matter present at Mars’ surface is the logical source of these compounds. Nevertheless, this discovery of indigenous organic matter in the Mars regolith raises important questions: How do the oxychlorines influence the pyrolysis of organics? What are the organics precursors of the organo‐chlorinated molecules detected on Mars? Is there a way to identify the parent molecules in a sample after pyrolysis? This paper presents the results of systematic laboratory experiments of the products formed during the pyrolysis of organic compounds from three chemical families—polycyclic aromatic hydrocarbons (PAHs), amino acids and carboxylic acids—in presence of calcium perchlorates. Results show that the PAH parent molecules and most of the carboxylic acids are still detectable after pyrolysis in presence of calcium perchlorate and that the degradation and/or evolution of all parent molecules mostly depends on their chemical nature. In addition, we demonstrate that the chlorohydrocarbons detected on Mars by the SAM instrument could come from the three chemical families studied.

Few traces of Earth’s geologic record are preserved from the time of life’s emergence, over 3,800 million years ago. Consequently, what little we understand about abiogenesis — the origin of life on Earth — is based primarily on laboratory experiments and theory. The best geological lens for understanding early Earth might actually come from Mars, a planet with a crust that’s overall far more ancient than our own. On Earth, surface sedimentary environments are thought to best preserve evidence of ancient life, but this is mostly because our planet has been dominated by high photosynthetic biomass production at the surface for the last ~2,500 million years or more. By the time oxygenic photosynthesis evolved on Earth, Mars had been a hyperarid, frozen desert with a surface bombarded by high-energy solar and cosmic radiation for more than a billion years, and as a result, photosynthetic surface life may never have occurred on Mars. Therefore, one must question whether searching for evidence of life in Martian surface sediments is the best strategy. This Perspective explores the possibility that the abundant hydrothermal environments on Mars might provide more valuable insights into life’s origins. Ancient hydrothermal deposits formed in the Martian subsurface may be the best targets for finding evidence for ancient life on Mars, and clues about the origin of life on Earth.

The Sample Analysis at Mars (SAM) experiment on the National Aeronautics and Space Administration Curiosity rover seeks evidence of organic compounds on the surface of Mars. Since the beginning of the mission, various organic molecules have been detected and identified. While several have been demonstrated to be indigenous to the Martian soil and rocks analyzed, others appear to have been produced from sources internal to the experiment. The objective of this study is to build an exhaustive molecular database to support the interpretation of SAM results by identifying all the chemical species produced from Tenax® adsorbents, by determining (1) the thermal degradation by‐products of Tenax®, (2) the effect of Tenax® conditioning on the formation of Tenax® by‐products, (3) the impact of MTBSTFA or a mixture of MTBSTFA and DMF on Tenax® decomposition, and (4) the reaction between Tenax® and calcium perchlorate. Our results indicate that the by‐products of the SAM trap are due to the impact of trap heating, the impact of the derivatization reagent (MTBSTFA) and the presence of perchlorate in Martian soil. Some of these by‐products are observed in the SAM gas chromatograph mass spectrometer data from Mars.

Concretions are prevalent features in the generally lacustrine deposits of the Murray formation in Gale crater. In this work, we document the morphologic, textural, and chemical properties of these concretions throughout 300 m of Murray formation stratigraphy from Mars Science Laboratory observations between Sols 750–1900. We interpret these observations to constrain the timing and composition of post-depositional fluid events at Gale crater. We determine that the overall diversity of concretion morphology, size, texture, and chemistry throughout the Murray formation indicates that concretions formed in multiple, likely late diagenetic, episodes with varying fluid chemistries. Four major concretion assemblages are observed at distinct stratigraphic intervals and approximately correlate with major distinct chemical enrichments in Mg-S-Ni-Cl, Mn-P, and Ca-S, among other local enrichments. Different concretion size populations and complex relationships between concretions and veins also suggest multiple precipitation events at Gale crater. Many concretions likely formed during late diagenesis after sediment compaction and lithification, based on observations of concretions preserving primary host rock laminations without differential compaction. An upsection decrease in overall concretion size corresponds to an inferred upsection decrease in porosity and permeability, thus constraining concretion formation as postdating fluid events that produced initial cementation and porosity loss. The combined observations of late diagenetic concretions and distinct chemical enrichments related to concretions allow constraints to be placed on the chemistry of late stage fluids at Gale crater. Collectively, concretion observations from this work and previous studies of other diagenetic features (veins, alteration halos) suggest at least six post-depositional events that occurred at Gale crater after the deposition of the Murray formation.

The search for life beyond Earth is a key motivator in space exploration. Informational polymers, like DNA and RNA, are key biosignatures for life as we know it. The MinION is a miniature DNA sequencer based on versatile nanopore technology that could be implemented on future planetary missions. A critical unanswered question is whether the MinION and its protein-based nanopores can withstand increased radiation exposure outside Earth’s shielding magnetic field. We evaluated the effects of ionizing radiation on the MinION platform – including flow cells, reagents, and hardware – and discovered limited performance loss when exposed to ionizing doses comparable to a mission to Mars. Targets with harsher radiation environments, like Europa, would require improved radiation resistance via additional shielding or design refinements.

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.

The extremely cold and arid conditions of Antarctica make it uniquely positioned to investigate fundamental questions regarding the persistence of life in extreme environments. Within the McMurdo Dry Valleys and surrounding mountain ranges are multiple ancient relict lakes, paleolakes, with lacustrine deposits spanning from thousands to millions of years in age. Here we present data from light microscopy, scanning electron microscopy, electron dispersive x-ray spectroscopy, and radiocarbon dating to catalog the remarkable range of life preserved within these deposits. This includes intact microbes and nanobacteria-sized cocci, CaCO3 precipitations consistent with biogenic calcium, previously undescribed net-like structures, possible dormant spores, and long-extinct yet exquisitely preserved non-vascular plants. These images provide an important reference for further microbiome investigations of Antarctic paleolake samples. In addition, these findings may provide a visual reference for the use of subsurface groundwater microbial communities as an analog for paleolake subsurface water on planets such as Mars.

© 2017 Macmillan Publishers Limited, part of Springer Nature. All rights reserved. Variability in the sulfur isotopic composition in sediments can reflect atmospheric, geologic and biological processes. Evidence for ancient fluvio-lacustrine environments at Gale crater on Mars and a lack of efficient crustal recycling mechanisms on the planet suggests a surface environment that was once warm enough to allow the presence of liquid water, at least for discrete periods of time, and implies a greenhouse effect that may have been influenced by sulfur-bearing volcanic gases. Here we report in situ analyses of the sulfur isotopic compositions of SO2volatilized from ten sediment samples acquired by NASA's Curiosity rover along a 13 km traverse of Gale crater. We find large variations in sulfur isotopic composition that exceed those measured for Martian meteorites and show both depletion and enrichment in34S. Measured values of Δ34S range from - 47 ± 14‰ to 28 ± 7‰, similar to the range typical of terrestrial environments. Although limited geochronological constraints on the stratigraphy traversed by Curiosity are available, we propose that the observed sulfur isotopic signatures at Gale crater can be explained by equilibrium fractionation between sulfate and sulfide in an impact-driven hydrothermal system and atmospheric processing of sulfur-bearing gases during transient warm periods.

Robotic balloons, also known as aerobots, have become candidates for collecting atmospheric data and detailed surface observations of Venus, Mars, and Titan. A mission to Venus over a decade ago used two of them. Their inclusion last year in attempts by a balloonist to circumnavigate the Earth aptly demonstrated their utility for remote sensing and in situ observations of planetary atmospheres. To simulate aspects of an aerobot mission, a small payload to measure local atmospheric conditions and balloon position and velocity was included on Solo Spirit “Round the World” flights during January and August of last year. These missions, flown in Roziere balloons, were attempts by Steve Fossett to become the first person to circumnavigate the globe in a balloon without stopping. Neither attempt was successful, but the aerobot came through with flying colors.

[1] There is increasing evidence that sulfur played an important role on early Mars. Sulfur is distributed ubiquitously on the Martian surface, and sulfur in Martian meteorites carries the signature of atmospheric interactions. Recent work suggests that the radiative properties of sulfur volatiles that were degassed into the Martian atmosphere may have caused a greenhouse effect early in the planet's history. It remains unclear, however, over what timescales warming from sulfur volatiles would have persisted, and consequently how significant this warming may have been. While most photochemistry research to date has concentrated on current Martian conditions, the ancient Martian atmosphere was thicker, warmer, and more reducing than the current regime. Here we investigate sulfur photochemistry in a 500 mb ancient Martian atmosphere. After adapting a model used to study sulfur photochemistry on Earth during the Archean, we find a short lifetime for SO2 in the current Martian atmosphere, similar to results of other photochemical studies. However, our simulations suggest that moderate mixing ratios of SO2 (10−8 ≤ f(SO2) ≤ 10−6) could have persisted in the ancient Martian atmosphere for hundreds of years, generating short but potent warming events following episodes of volcanic activity.

[1] Mineralogical, geological, geophysical, and isotopic data recently returned from Mars suggest that the delivery of sulfur gases to the atmosphere may have played a significant role in the planet's early evolution. Using the Gusev Crater basalt composition and a batch melting model, we obtain a high sulfur solubility, approximately 1400 ppm, in Martian mantle melts. We proceed to explore different scenarios for the pulsed degassing of sulfur volatiles associated with the emplacement of near-surface dikes during the late Noachian or early Hesperian, when surface pressures are thought to be substantially higher than present. We investigate background Martian atmospheres of 50 and 500 mbar CO2 with varying abundances of H2O and sulfur volatiles (H2S and SO2 mixing ratios of 10−3 to 10−6). Results suggest that these sulfur volatile influxes, alone, could have been responsible for greenhouse warming up to 25 K above that caused by CO2. Including additional water vapor feedback, this process could have raised the early surface temperature above the freezing point for brines and possibly allowed transient liquid water on the Martian surface. Each temperature rise was likely to have been short-lived, however, due to brief residence times for sulfur volatiles in an optically thin atmosphere.

The Microscopic Imager (MI) on the Mars Exploration Rover Spirit has returned images of Mars with higher resolution than any previous camera system, allowing detailed petrographic and sedimentological studies of the rocks and soils at the Gusev landing site. Designed to simulate a geologist's hand lens, the MI is mounted on Spirit's instrument arm and can resolve objects 0.1 mm in size or larger. This paper provides an overview of MI operations, data calibration, processing, and analysis of MI data returned during the first 450 sols (Mars days) of the Spirit landed mission. The primary goal of this paper is to facilitate further analyses of MI data by summarizing the methods used to acquire and process the data, the radiometric and geometric accuracy of MI data products, and the availability of archival products. In addition, scientific results of the MI investigation are summarized. MI observations show that poorly sorted soils are common in Gusev crater, although aeolian bedforms have well-sorted coarse sand grains on their surfaces. Abraded surfaces of plains rocks show igneous textures, light-toned veins or fracture-filling minerals, and discrete coatings. The rocks in the Columbia Hills have a wide variety of granular textures, consistent with volcaniclastic or impact origins. Case hardening and submillimeter veins observed in the rocks as well as soil crusts and cemented clods imply episodic subsurface aqueous fluid movement, which has altered multiple geologic units in the Columbia Hills. The MI also monitored Spirit's solar panels and the magnets on the rover's deck.