Organic carbon concentrations in 3.5-billion-year-old lacustrine mudstones of Mars.

The Sample Analysis at Mars instrument stepped combustion experiment on a Yellowknife Bay mudstone at Gale crater, Mars revealed the presence of organic carbon of Martian and meteoritic origins. The combustion experiment was designed to access refractory organic carbon in Mars surface sediments by heating samples in the presence of oxygen to combust carbon to CO2. Four steps were performed, two at low temperatures (less than ∼550 °C) and two at high temperatures (up to ∼870 °C). More than 950 µg C/g was released at low temperatures (with an isotopic composition of δ13C = +1.5 ± 3.8‰) representing a minimum of 431 µg C/g indigenous organic and inorganic Martian carbon components. Above 550 °C, 273 ± 30 µg C/g was evolved as CO2 and CO (with estimated δ13C = -32.9‰ to -10.1‰ for organic carbon). The source of high temperature organic carbon cannot be definitively confirmed by isotopic composition, which is consistent with macromolecular organic carbon of igneous origin, meteoritic infall, or diagenetically altered biomass, or a combination of these. If from allochthonous deposition, organic carbon could have supported both prebiotic organic chemistry and heterotrophic metabolism at Gale crater, Mars, at ∼3.5 Ga.

Science Objectives for Flagship-Class Mission Concepts for the Search for Evidence of Life at Enceladus.

Cassini revealed that Saturn's Moon Enceladus hosts a subsurface ocean that meets the accepted criteria for habitability with bio-essential elements and compounds, liquid water, and energy sources available in the environment. Whether these conditions are sufficiently abundant and collocated to support life remains unknown and cannot be determined from Cassini data. However, thanks to the plume of oceanic material emanating from Enceladus' south pole, a new mission to Enceladus could search for evidence of life without having to descend through kilometers of ice. In this article, we outline the science motivations for such a successor to Cassini, choosing the primary science goal to be determining whether Enceladus is inhabited and assuming a resource level equivalent to NASA's Flagship-class missions. We selected a set of potential biosignature measurements that are complementary and orthogonal to build a robust case for any life detection result. This result would be further informed by quantifications of the habitability of the environment through geochemical and geophysical investigations into the ocean and ice shell crust. This study demonstrates that Enceladus' plume offers an unparalleled opportunity for in situ exploration of an Ocean World and that the planetary science and astrobiology community is well equipped to take full advantage of it in the coming decades.

Depleted carbon isotope compositions observed at Gale crater, Mars.

Obtaining carbon isotopic information for organic carbon from Martian sediments has long been a goal of planetary science, as it has the potential to elucidate the origin of such carbon and aspects of Martian carbon cycling. Carbon isotopic values (δ13CVPDB) of the methane released during pyrolysis of 24 powder samples at Gale crater, Mars, show a high degree of variation (-137 ± 8‰ to +22 ± 10‰) when measured by the tunable laser spectrometer portion of the Sample Analysis at Mars instrument suite during evolved gas analysis. Included in these data are 10 measured δ13C values less than -70‰ found for six different sampling locations, all potentially associated with a possible paleosurface. There are multiple plausible explanations for the anomalously depleted 13C observed in evolved methane, but no single explanation can be accepted without further research. Three possible explanations are the photolysis of biological methane released from the subsurface, photoreduction of atmospheric CO2, and deposition of cosmic dust during passage through a galactic molecular cloud. All three of these scenarios are unconventional, unlike processes common on Earth.

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.

Influence of Calcium Perchlorate on the Search for Organics on Mars with Tetramethylammonium Hydroxide Thermochemolysis.

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.

First Detections of Dichlorobenzene Isomers and Trichloromethylpropane from Organic Matter Indigenous to Mars Mudstone in Gale Crater, Mars: Results from the Sample Analysis at Mars Instrument Onboard the Curiosity Rover.

Chromatographic analysis of the Cumberland mudstone in Gale crater by the Sample Analysis at Mars (SAM) instrument revealed the detection of two to three isomers of dichlorobenzene. Their individual concentrations were estimated to be in the 0.5-17 ppbw range relative to the sample mass. We also report the first detection of trichloromethylpropane and the confirmation of the detection of chlorobenzene previously reported. Supporting laboratory experiments excluded the SAM internal background as the source of those compounds, thus confirming the organic carbon and chlorine of the newly detected chlorohydrocarbons are indigenous to the mudstone sample. Laboratory experiments also demonstrated that the chlorohydrocarbons were mainly produced from chemical reactions occurring in the SAM ovens between organic molecules and oxychlorines contained in the sample. The results we obtained show that meteoritic organics and tested chemical species (a polycyclic aromatic hydrocarbon, an amino acid, and a carboxylic acid) were plausible organic precursors of the chlorinated aromatic molecules detected with SAM, thus suggesting that they could be among the organic molecules present in the mudstone. Results from this study coupled with previously reported detections of chlorinated aromatics (<300 ppbw) indigenous to the same mudstone highlight that organics can be preserved from the harsh surface conditions even at shallow depth. The detection of new chlorohydrocarbons with SAM confirms that organic molecules should have been available in an environment favorable to life forms, strengthening the habitability aspect of Gale crater.

Constraints on the Metabolic Activity of Microorganisms in Atacama Surface Soils Inferred from Refractory Biomarkers: Implications for Martian Habitability and Biomarker Detection.

Dryness is one of the main environmental challenges to microbial survival. Understanding the threshold of microbial tolerance to extreme dryness is relevant to better constrain the environmental limits of life on Earth and critically evaluate long-term habitability models of Mars. Biomolecular proxies for microbial adaptation and growth were measured in Mars-like hyperarid surface soils in the Atacama Desert that experience only a few millimeters of precipitation per decade, and in biologically active soils a few hundred kilometers away that experience two- to fivefold more precipitation. Diversity and abundance of lipids and other biomolecules decreased with increasing dryness. Cyclopropane fatty acids (CFAs), which are indicative of adaptive response to environmental stress and growth in bacteria, were only detected in the wetter surface soils. The ratio of trans to cis isomers of an unsaturated fatty acid, another bacterial stress indicator, decreased with increasingly dry conditions. Aspartic acid racemization ratios increased from 0.01 in the wetter soils to 0.1 in the driest soils, which is indicative of racemization rates comparable to de novo biosynthesis over long timescales (∼10,000 years). The content and integrity of stress proteins profiled by immunoassays were additional indicators that biomass in the driest soils is not recycled at significant levels. Together, our results point to minimal or no in situ microbial growth in the driest surface soils of the Atacama, and any metabolic activity is likely to be basal for cellular repair and maintenance only. Our data add to a growing body of evidence that the driest Atacama surface soils represent a threshold for long-term habitability (i.e., growth and reproduction). These results place constraints on the potential for extant life on the surface of Mars, which is 100-1000 times drier than the driest regions in the Atacama. Key Words: Atacama Desert-Dryness-Growth-Habitability-Biomarker-Mars. Astrobiology 18, 955-966.

Organic matter preserved in 3-billion-year-old mudstones at Gale crater, Mars.

Establishing the presence and state of organic matter, including its possible biosignatures, in martian materials has been an elusive quest, despite limited reports of the existence of organic matter on Mars. We report the in situ detection of organic matter preserved in lacustrine mudstones at the base of the ~3.5-billion-year-old Murray formation at Pahrump Hills, Gale crater, by the Sample Analysis at Mars instrument suite onboard the Curiosity rover. Diverse pyrolysis products, including thiophenic, aromatic, and aliphatic compounds released at high temperatures (500° to 820°C), were directly detected by evolved gas analysis. Thiophenes were also observed by gas chromatography-mass spectrometry. Their presence suggests that sulfurization aided organic matter preservation. At least 50 nanomoles of organic carbon persists, probably as macromolecules containing 5% carbon as organic sulfur molecules.

Background levels of methane in Mars' atmosphere show strong seasonal variations.

Variable levels of methane in the martian atmosphere have eluded explanation partly because the measurements are not repeatable in time or location. We report in situ measurements at Gale crater made over a 5-year period by the Tunable Laser Spectrometer on the Curiosity rover. The background levels of methane have a mean value 0.41 ± 0.16 parts per billion by volume (ppbv) (95% confidence interval) and exhibit a strong, repeatable seasonal variation (0.24 to 0.65 ppbv). This variation is greater than that predicted from either ultraviolet degradation of impact-delivered organics on the surface or from the annual surface pressure cycle. The large seasonal variation in the background and occurrences of higher temporary spikes (~7 ppbv) are consistent with small localized sources of methane released from martian surface or subsurface reservoirs.

Low Hesperian PCO2 constrained from in situ mineralogical analysis at Gale Crater, Mars.

Carbon dioxide is an essential atmospheric component in martian climate models that attempt to reconcile a faint young sun with planetwide evidence of liquid water in the Noachian and Early Hesperian. In this study, we use mineral and contextual sedimentary environmental data measured by the Mars Science Laboratory (MSL) Rover Curiosity to estimate the atmospheric partial pressure of CO2 (PCO2) coinciding with a long-lived lake system in Gale Crater at ∼3.5 Ga. A reaction-transport model that simulates mineralogy observed within the Sheepbed member at Yellowknife Bay (YKB), by coupling mineral equilibria with carbonate precipitation kinetics and rates of sedimentation, indicates atmospheric PCO2 levels in the 10s mbar range. At such low PCO2 levels, existing climate models are unable to warm Hesperian Mars anywhere near the freezing point of water, and other gases are required to raise atmospheric pressure to prevent lake waters from being lost to the atmosphere. Thus, either lacustrine features of Gale formed in a cold environment by a mechanism yet to be determined, or the climate models still lack an essential component that would serve to elevate surface temperatures, at least locally, on Hesperian Mars. Our results also impose restrictions on the potential role of atmospheric CO2 in inferred warmer conditions and valley network formation of the late Noachian.

Xeropreservation of functionalized lipid biomarkers in hyperarid soils in the Atacama Desert.

Our understanding of long-term organic matter preservation comes mostly from studies in aquatic systems. In contrast, taphonomic processes in extremely dry environments are relatively understudied and are poorly understood. We investigated the accumulation and preservation of lipid biomarkers in hyperarid soils in the Yungay region of the Atacama Desert. Lipids from seven soil horizons in a 2.5 m vertical profile were extracted and analyzed using GC-MS and LC-MS. Diagnostic functionalized lipids and geolipids were detected and increased in abundance and diversity with depth. Deeper clay units contain fossil organic matter (radiocarbon dead) that has been protected from rainwater since the onset of hyperaridity. We show that these clay units contain lipids in an excellent state of structural preservation with functional groups and unsaturated bonds in carbon chains. This indicates that minimal degradation of lipids has occurred in these soils since the time of their deposition between >40,000 and 2 million years ago. The exceptional structural preservation of biomarkers is likely due to the long-term hyperaridity that has minimized microbial and enzymatic activity, a taphonomic process we term xeropreservation (i.e. preservation by drying). The degree of biomarker preservation allowed us to reconstruct major changes in ecology in the Yungay region that reflect a shift in hydrological regime from wet to dry since the early Quaternary. Our results suggest that hyperarid environments, which comprise 7.5% of the continental landmass, could represent a rich and relatively unexplored source of paleobiological information on Earth.

Evidence for indigenous nitrogen in sedimentary and aeolian deposits from the Curiosity rover investigations at Gale crater, Mars.

The Sample Analysis at Mars (SAM) investigation on the Mars Science Laboratory (MSL) Curiosity rover has detected oxidized nitrogen-bearing compounds during pyrolysis of scooped aeolian sediments and drilled sedimentary deposits within Gale crater. Total N concentrations ranged from 20 to 250 nmol N per sample. After subtraction of known N sources in SAM, our results support the equivalent of 110-300 ppm of nitrate in the Rocknest (RN) aeolian samples, and 70-260 and 330-1,100 ppm nitrate in John Klein (JK) and Cumberland (CB) mudstone deposits, respectively. Discovery of indigenous martian nitrogen in Mars surface materials has important implications for habitability and, specifically, for the potential evolution of a nitrogen cycle at some point in martian history. The detection of nitrate in both wind-drifted fines (RN) and in mudstone (JK, CB) is likely a result of N2 fixation to nitrate generated by thermal shock from impact or volcanic plume lightning on ancient Mars. Fixed nitrogen could have facilitated the development of a primitive nitrogen cycle on the surface of ancient Mars, potentially providing a biochemically accessible source of nitrogen.

Mars atmosphere. Mars methane detection and variability at Gale crater.

Reports of plumes or patches of methane in the martian atmosphere that vary over monthly time scales have defied explanation to date. From in situ measurements made over a 20-month period by the tunable laser spectrometer of the Sample Analysis at Mars instrument suite on Curiosity at Gale crater, we report detection of background levels of atmospheric methane of mean value 0.69 ± 0.25 parts per billion by volume (ppbv) at the 95% confidence interval (CI). This abundance is lower than model estimates of ultraviolet degradation of accreted interplanetary dust particles or carbonaceous chondrite material. Additionally, in four sequential measurements spanning a 60-sol period (where 1 sol is a martian day), we observed elevated levels of methane of 7.2 ± 2.1 ppbv (95% CI), implying that Mars is episodically producing methane from an additional unknown source.

The origin and implications of clay minerals from Yellowknife Bay, Gale crater, Mars.

The Mars Science Laboratory (MSL) rover Curiosity has documented a section of fluvio-lacustrine strata at Yellowknife Bay (YKB), an embayment on the floor of Gale crater, approximately 500 m east of the Bradbury landing site. X-ray diffraction (XRD) data and evolved gas analysis (EGA) data from the CheMin and SAM instruments show that two powdered mudstone samples (named John Klein and Cumberland) drilled from the Sheepbed member of this succession contain up to ~20 wt% clay minerals. A trioctahedral smectite, likely a ferrian saponite, is the only clay mineral phase detected in these samples. Smectites of the two samples exhibit different 001 spacing under the low partial pressures of H2O inside the CheMin instrument (relative humidity <1%). Smectite interlayers in John Klein collapsed sometime between clay mineral formation and the time of analysis to a basal spacing of 10 Å, but largely remain open in the Cumberland sample with a basal spacing of ~13.2 Å. Partial intercalation of Cumberland smectites by metal-hydroxyl groups, a common process in certain pedogenic and lacustrine settings on Earth, is our favored explanation for these differences. The relatively low abundances of olivine and enriched levels of magnetite in the Sheepbed mudstone, when compared with regional basalt compositions derived from orbital data, suggest that clay minerals formed with magnetite in situ via aqueous alteration of olivine. Mass-balance calculations are permissive of such a reaction. Moreover, the Sheepbed mudstone mineral assemblage is consistent with minimal inputs of detrital clay minerals from the crater walls and rim. Early diagenetic fabrics suggest clay mineral formation prior to lithification. Thermodynamic modeling indicates that the production of authigenic magnetite and saponite at surficial temperatures requires a moderate supply of oxidants, allowing circum-neutral pH. The kinetics of olivine alteration suggest the presence of fluids for thousands to hundreds of thousands of years. Mineralogical evidence of the persistence of benign aqueous conditions at YKB for extended periods indicates a potentially habitable environment where life could establish itself. Mediated oxidation of Fe2+ in olivine to Fe3+ in magnetite, and perhaps in smectites provided a potential energy source for organisms.

Mars' surface radiation environment measured with the Mars Science Laboratory's Curiosity rover.

The Radiation Assessment Detector (RAD) on the Mars Science Laboratory's Curiosity rover began making detailed measurements of the cosmic ray and energetic particle radiation environment on the surface of Mars on 7 August 2012. We report and discuss measurements of the absorbed dose and dose equivalent from galactic cosmic rays and solar energetic particles on the martian surface for ~300 days of observations during the current solar maximum. These measurements provide insight into the radiation hazards associated with a human mission to the surface of Mars and provide an anchor point with which to model the subsurface radiation environment, with implications for microbial survival times of any possible extant or past life, as well as for the preservation of potential organic biosignatures of the ancient martian environment.

Preservation of martian organic and environmental records: final report of the Mars biosignature working group.

The Mars Science Laboratory (MSL) has an instrument package capable of making measurements of past and present environmental conditions. The data generated may tell us if Mars is, or ever was, able to support life. However, the knowledge of Mars' past history and the geological processes most likely to preserve a record of that history remain sparse and, in some instances, ambiguous. Physical, chemical, and geological processes relevant to biosignature preservation on Earth, especially under conditions early in its history when microbial life predominated, are also imperfectly known. Here, we present the report of a working group chartered by the Co-Chairs of NASA's MSL Project Science Group, John P. Grotzinger and Michael A. Meyer, to review and evaluate potential for biosignature formation and preservation on Mars. Orbital images confirm that layered rocks achieved kilometer-scale thicknesses in some regions of ancient Mars. Clearly, interplays of sedimentation and erosional processes govern present-day exposures, and our understanding of these processes is incomplete. MSL can document and evaluate patterns of stratigraphic development as well as the sources of layered materials and their subsequent diagenesis. It can also document other potential biosignature repositories such as hydrothermal environments. These capabilities offer an unprecedented opportunity to decipher key aspects of the environmental evolution of Mars' early surface and aspects of the diagenetic processes that have operated since that time. Considering the MSL instrument payload package, we identified the following classes of biosignatures as within the MSL detection window: organism morphologies (cells, body fossils, casts), biofabrics (including microbial mats), diagnostic organic molecules, isotopic signatures, evidence of biomineralization and bioalteration, spatial patterns in chemistry, and biogenic gases. Of these, biogenic organic molecules and biogenic atmospheric gases are considered the most definitive and most readily detectable by MSL.

Late Archean rise of aerobic microbial ecosystems.

We report the (13)C content of preserved organic carbon for a 150 million-year section of late Archean shallow and deepwater sediments of the Hamersley Province in Western Australia. We find a (13)C enrichment of approximately 10 per thousand in organic carbon of post-2.7-billion-year-old shallow-water carbonate rocks relative to deepwater sediments. The shallow-water organic-carbon (13)C content has a 29 per thousand range in values (-57 to -28 per thousand), and it contrasts with the less variable but strongly (13)C-depleted (-40 to -45 per thousand) organic carbon in deepwater sediments. The (13)C enrichment likely represents microbial habitats not as strongly influenced by assimilation of methane or other (13)C-depleted substrates. We propose that continued oxidation of shallow settings favored the expansion of aerobic ecosystems and respiring organisms, and, as a result, isotopic signatures of preserved organic carbon in shallow settings approached that of photosynthetic biomass. Facies analysis of published carbon-isotopic records indicates that the Hamersley shallow-water signal may be representative of a late Archean global signature and that it preceded a similar, but delayed, (13)C enrichment of deepwater deposits. The data suggest that a global-scale expansion of oxygenated habitats accompanied the progression away from anaerobic ecosystems toward respiring microbial communities fueled by oxygenic photosynthesis before the oxygenation of the atmosphere after 2.45 billion years ago.