Complex organosulfur molecules on comet 67P: Evidence from the ROSINA measurements and insights from laboratory simulations.

The ROSINA (Rosetta Orbiter Spectrometer for Ion and Neutral Analysis) instrument aboard the Rosetta mission revolutionized our understanding of cometary material composition. One of Rosetta's key findings is the complexity of the composition of comet 67P/Churyumov-Gerasimenko. Here, we used ROSINA data to analyze dust particles that were volatilized during a dust event in September 2016 and report the detection of large organosulfur species and an increase in the abundances of sulfurous species previously detected in the coma. Our data support the presence of complex sulfur-bearing organics on the surface of the comet. In addition, we conducted laboratory simulations that show that this material may have formed from chemical reactions that were initiated by the irradiation of mixed ices containing H2S. Our findings highlight the importance of sulfur chemistry in cometary and precometary materials and the possibility of characterizing organosulfur materials in other comets and small icy bodies using the James Webb Space Telescope.

Aqueous alteration processes in Jezero crater, Mars-implications for organic geochemistry.

The Perseverance rover landed in Jezero crater, Mars, in February 2021. We used the Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) instrument to perform deep-ultraviolet Raman and fluorescence spectroscopy of three rocks within the crater. We identify evidence for two distinct ancient aqueous environments at different times. Reactions with liquid water formed carbonates in an olivine-rich igneous rock. A sulfate-perchlorate mixture is present in the rocks, which probably formed by later modifications of the rocks by brine. Fluorescence signatures consistent with aromatic organic compounds occur throughout these rocks and are preserved in minerals related to both aqueous environments.

Geological, multispectral, and meteorological imaging results from the Mars 2020 Perseverance rover in Jezero crater.

Perseverance's Mastcam-Z instrument provides high-resolution stereo and multispectral images with a unique combination of spatial resolution, spatial coverage, and wavelength coverage along the rover's traverse in Jezero crater, Mars. Images reveal rocks consistent with an igneous (including volcanic and/or volcaniclastic) and/or impactite origin and limited aqueous alteration, including polygonally fractured rocks with weathered coatings; massive boulder-forming bedrock consisting of mafic silicates, ferric oxides, and/or iron-bearing alteration minerals; and coarsely layered outcrops dominated by olivine. Pyroxene dominates the iron-bearing mineralogy in the fine-grained regolith, while olivine dominates the coarse-grained regolith. Solar and atmospheric imaging observations show significant intra- and intersol variations in dust optical depth and water ice clouds, as well as unique examples of boundary layer vortex action from both natural (dust devil) and Ingenuity helicopter-induced dust lifting. High-resolution stereo imaging also provides geologic context for rover operations, other instrument observations, and sample selection, characterization, and confirmation.

Mid- and long-wave infrared point spectrometer (MLPS): a miniature space-borne science instrument.

The mid- and long-wave infrared point spectrometer (MLPS) is an infrared point spectrometer that utilizes unique technologies to meet the spectral coverage, spectral sampling, and field-of-view (FOV) requirements of many future space-borne missions in a small volume with modest power consumption. MLPS simultaneously acquires high resolution mid-wave infrared (∼2-4 µm) and long-wave infrared (∼5.5-11 µm) measurements from a single, integrated instrument. The broadband response of MLPS can measure spectroscopically resolved reflected and thermally emitted radiation from a wide range of targets and return compositional, mineralogic, and thermophysical science from a single data set. We have built a prototype MLPS and performed end-to-end testing under vacuum showing that the measured spectral response and the signal-to-noise ratio (SNR) for both the mid-wave infrared (MIR) and long-wave infrared (LIR) channels of MLPS agree with established instrument models.

Tracing Carbonate Formation, Serpentinization, and Biological Materials With Micro-/Meso-Scale Infrared Imaging Spectroscopy in a Mars Analog System, Samail Ophiolite, Oman.

Visible-shortwave infrared (VSWIR) imaging spectrometers map composition remotely with spatial context, typically at many meters-scale from orbital and airborne data. Here, we evaluate VSWIR imaging spectroscopy capabilities at centimeters to sub-millimeter scale at the Samail Ophiolite, Oman, where mafic and ultramafic lithologies and their alteration products, including serpentine and carbonates, are exposed in a semi-arid environment, analogous to similar mineral associations observed from Mars orbit that will be explored by the Mars-2020 rover. At outcrop and hand specimen scales, VSWIR spectroscopy (a) identifies cross-cutting veins of calcite, dolomite, magnesite, serpentine, and chlorite that record pathways and time-order of multiple alteration events of changing fluid composition; (b) detects small-scale, partially altered remnant pyroxenes and localized epidote and prehnite that indicate protolith composition and temperatures and pressures of multiple generations of faulting and alteration, respectively; and (c) discriminates between spectrally similar carbonate and serpentine phases and carbonate solid solutions. In natural magnesite veins, minor amounts of ferrous iron can appear similar to olivine's strong 1-µm absorption, though no olivine is present. We also find that mineral identification for carbonate and serpentine in mixtures with each other is strongly scale- and texture-dependent; ∼40 area% dolomite in mm-scale veins at one serpentinite outcrop and ∼18 area% serpentine in a calcite-rich travertine outcrop are not discriminated until spatial scales of <∼1-2 cm/pixel. We found biological materials, for example bacterial mats versus vascular plants, are differentiated using wavelengths <1 µm while shortwave infrared wavelengths >1 µm are required to identify most organic materials and distinguish most mineral phases.

Hydrothermal Alteration of the Ocean Crust and Patterns in Mineralization With Depth as Measured by Micro-Imaging Infrared Spectroscopy.

Processes for formation, cooling, and altering Earth's ocean crust are not yet completely understood due to challenges in access and sampling. Here, we use contiguous micro-imaging infrared spectroscopy to develop complete-core maps of mineral occurrence and investigate spatial patterns in the hydrothermal alteration of 1.2 km of oceanic crust recovered from Oman Drilling Project Holes GT1A, GT2A, and GT3A drilled in the Samail Ophiolite, Oman. The imaging spectrometer shortwave infrared sensor measured reflectance of light at wavelengths 1.0-2.6 µm at 250-260 µm/pixel, resulting in >1 billion independent measurements. We map distributions of nine key primary and secondary minerals/mineral groups-clinopyroxene, amphibole, calcite, chlorite, epidote, gypsum, kaolinite/montmorillonite, prehnite, and zeolite-and find differences in their spatial occurrences and pervasiveness. Accuracy of spectral mapping of occurrence is 68%-100%, established using X-ray diffraction measurements from the core description. The sheeted dikes and gabbros of upper oceanic crust Hole GT3A show more pervasive alteration and alteration dominated by chlorite, amphibole, and epidote. The foliated/layered gabbros of GT2A from intermediate crustal depths have similarly widespread chlorite but more zeolite and little amphibole and epidote. The layered gabbros of the lower oceanic crust (GT1A) have remnant pyroxene and 2X less chlorite, but alteration is extensive within and surrounding major fault zones with widespread occurrences of amphibole. The results indicate greater distribution of higher temperature alteration minerals in the upper oceanic crust relative to deeper gabbros and highlight the importance of fault zones in hydrothermal convection in the lower ocean crust.

Formation of Magnesium Carbonates on Earth and Implications for Mars.

Magnesium carbonates have been identified within the landing site of the Perseverance rover mission. This study reviews terrestrial analog environments and textural, mineral assemblage, isotopic, and elemental analyses that have been applied to establish formation conditions of magnesium carbonates. Magnesium carbonates form in five distinct settings: ultramafic rock-hosted veins, the matrix of carbonated peridotite, nodules in soil, alkaline lake, and playa deposits, and as diagenetic replacements within lime-and dolostones. Dominant textures include fine-grained or microcrystalline veins, nodules, and crusts. Microbial influences on formation are recorded in thrombolites, stromatolites, crinkly, and pustular laminites, spheroids, and filamentous microstructures. Mineral assemblages, fluid inclusions, and carbon, oxygen, magnesium, and clumped isotopes of carbon and oxygen have been used to determine the sources of carbon, magnesium, and fluid for magnesium carbonates as well as their temperatures of formation. Isotopic signatures in ultramafic rock-hosted magnesium carbonates reveal that they form by either low-temperature meteoric water infiltration and alteration, hydrothermal alteration, or metamorphic processes. Isotopic compositions of lacustrine magnesium carbonate record precipitation from lake water, evaporation processes, and ambient formation temperatures. Assessment of these features with similar analytical techniques applied to returned Martian samples can establish whether carbonates on ancient Mars were formed at high or low temperature conditions in the surface or subsurface through abiotic or biotic processes. The timing of carbonate formation processes could be constrained by 147Sm-143Nd isochron, U-Pb concordia, 207Pb-206Pb isochron radiometric dating as well as 3He, 21Ne, 22Ne, or 36Ar surface exposure dating of returned Martian magnesium carbonate samples.

Composition, Stratigraphy, and Geological History of the Noachian Basement Surrounding the Isidis Impact Basin.

The western part of the Isidis basin structure hosts a well-characterized Early Noachian to Amazonian stratigraphy. The Noachian Basement comprises its oldest exposed rocks (Early to Mid-Noachian) and was previously considered a single low-Ca pyroxenes (LCP)- and Fe/Mg-smectite-bearing unit. Here, we divide the Noachian Basement Group into five distinct geological units (Stratified Basement Unit, Blue Fractured Unit, Mixed Lithology Plains Unit, LCP-bearing Plateaus Unit, and Fe/Mg-smectite-bearing Mounds Unit), two geomorphological features (megabreccia and ridges), and a mineral deposit (kaolinite-bearing bright materials), based on geomorphology, spectral characteristics, and stratigraphic relationships. Megabreccia contain four different pre-Isidis lithologies, possibly including deeper crust or mantle materials, formed through mass wasting associated with transient crater collapse during Isidis basin formation. The Fe/Mg-smectite-bearing Stratified Basement Unit and LCP-bearing Blue Fractured Unit likewise represent pre-Isidis units within the Noachian Basement Group. Multiple Fe/Mg-smectite-bearing geological units with different stratigraphic positions and younger kaolinite-bearing bright materials indicate several aqueous alteration episodes of different ages and styles. Units with slight changes in pyroxene spectral properties suggest a transition from low-Ca pyroxene-containing materials to those with higher proportions of pyroxenes higher in Ca and/or glass that could be related to different impact and/or igneous processes, or provenance. This long history of Noachian and potentially Pre-Noachian geological processes, including impact basin formation, aqueous alteration, and multiple igneous and sedimentary petrogeneses, records changing ancient Mars environmental conditions. All units defined by this study are available 20 km outside of Jezero crater for in situ analysis and sampling during a potential extended mission scenario for the Mars 2020 rover.

Methane on Mars and Habitability: Challenges and Responses.

Recent measurements of methane (CH4) by the Mars Science Laboratory (MSL) now confront us with robust data that demand interpretation. Thus far, the MSL data have revealed a baseline level of CH4 (∼0.4 parts per billion by volume [ppbv]), with seasonal variations, as well as greatly enhanced spikes of CH4 with peak abundances of ∼7 ppbv. What do these CH4 revelations with drastically different abundances and temporal signatures represent in terms of interior geochemical processes, or is martian CH4 a biosignature? Discerning how CH4 generation occurs on Mars may shed light on the potential habitability of Mars. There is no evidence of life on the surface of Mars today, but microbes might reside beneath the surface. In this case, the carbon flux represented by CH4 would serve as a link between a putative subterranean biosphere on Mars and what we can measure above the surface. Alternatively, CH4 records modern geochemical activity. Here we ask the fundamental question: how active is Mars, geochemically and/or biologically? In this article, we examine geological, geochemical, and biogeochemical processes related to our overarching question. The martian atmosphere and surface are an overwhelmingly oxidizing environment, and life requires pairing of electron donors and electron acceptors, that is, redox gradients, as an essential source of energy. Therefore, a fundamental and critical question regarding the possibility of life on Mars is, "Where can we find redox gradients as energy sources for life on Mars?" Hence, regardless of the pathway that generates CH4 on Mars, the presence of CH4, a reduced species in an oxidant-rich environment, suggests the possibility of redox gradients supporting life and habitability on Mars. Recent missions such as ExoMars Trace Gas Orbiter may provide mapping of the global distribution of CH4. To discriminate between abiotic and biotic sources of CH4 on Mars, future studies should use a series of diagnostic geochemical analyses, preferably performed below the ground or at the ground/atmosphere interface, including measurements of CH4 isotopes, methane/ethane ratios, H2 gas concentration, and species such as acetic acid. Advances in the fields of Mars exploration and instrumentation will be driven, augmented, and supported by an improved understanding of atmospheric chemistry and dynamics, deep subsurface biogeochemistry, astrobiology, planetary geology, and geophysics. Future Mars exploration programs will have to expand the integration of complementary areas of expertise to generate synergistic and innovative ideas to realize breakthroughs in advancing our understanding of the potential of life and habitable conditions having existed on Mars. In this spirit, we conducted a set of interdisciplinary workshops. From this series has emerged a vision of technological, theoretical, and methodological innovations to explore the martian subsurface and to enhance spatial tracking of key volatiles, such as CH4.

Nature, formation, and distribution of carbonates on Ceres.

Different carbonates have been detected on Ceres, and their abundance and spatial distribution have been mapped using a visible and infrared mapping spectrometer (VIR), the Dawn imaging spectrometer. Carbonates are abundant and ubiquitous across the surface, but variations in the strength and position of infrared spectral absorptions indicate variations in the composition and amount of these minerals. Mg-Ca carbonates are detected all over the surface, but localized areas show Na carbonates, such as natrite (Na2CO3) and hydrated Na carbonates (for example, Na2CO3·H2O). Their geological settings and accessory NH4-bearing phases suggest the upwelling, excavation, and exposure of salts formed from Na-CO3-NH4-Cl brine solutions at multiple locations across the planet. The presence of the hydrated carbonates indicates that their formation/exposure on Ceres' surface is geologically recent and dehydration to the anhydrous form (Na2CO3) is ongoing, implying a still-evolving body.

Clay mineral formation under oxidized conditions and implications for paleoenvironments and organic preservation on Mars.

Clay mineral-bearing locations have been targeted for martian exploration as potentially habitable environments and as possible repositories for the preservation of organic matter. Although organic matter has been detected at Gale Crater, Mars, its concentrations are lower than expected from meteoritic and indigenous igneous and hydrothermal reduced carbon. We conducted synthesis experiments motivated by the hypothesis that some clay mineral formation may have occurred under oxidized conditions conducive to the destruction of organics. Previous work has suggested that anoxic and/or reducing conditions are needed to synthesize the Fe-rich clay mineral nontronite at low temperatures. In contrast, our experiments demonstrated the rapid formation of Fe-rich clay minerals of variable crystallinity from aqueous Fe3+ with small amounts of aqueous Mg2+. Our results suggest that Fe-rich clay minerals such as nontronite can form rapidly under oxidized conditions, which could help explain low concentrations of organics within some smectite-containing rocks or sediments on Mars.

Tracing the fate of carbon and the atmospheric evolution of Mars.

The climate of Mars likely evolved from a warmer, wetter early state to the cold, arid current state. However, no solutions for this evolution have previously been found to satisfy the observed geological features and isotopic measurements of the atmosphere. Here we show that a family of solutions exist, invoking no missing reservoirs or loss processes. Escape of carbon via CO photodissociation and sputtering enriches heavy carbon ((13)C) in the Martian atmosphere, partially compensated by moderate carbonate precipitation. The current atmospheric (13)C/(12)C and rock and soil carbonate measurements indicate an early atmosphere with a surface pressure <1 bar. Only scenarios with large amounts of carbonate formation in open lakes permit higher values up to 1.8 bar. The evolutionary scenarios are fully testable with data from the MAVEN mission and further studies of the isotopic composition of carbonate in the Martian rock record through time.

Insights from the metagenome of an acid salt lake: the role of biology in an extreme depositional environment.

The extremely acidic brine lakes of the Yilgarn Craton of Western Australia are home to some of the most biologically challenging waters on Earth. In this study, we employed metagenomic shotgun sequencing to generate a microbial profile of the depositional environment associated with the sulfur-rich sediments of one such lake. Of the 1.5 M high-quality reads generated, 0.25 M were mapped to protein features, which in turn provide new insights into the metabolic function of this community. In particular, 45 diverse genes associated with sulfur metabolism were identified, the majority of which were linked to either the conversion of sulfate to adenylylsulfate and the subsequent production of sulfide from sulfite or the oxidation of sulfide, elemental sulfur, and thiosulfate via the sulfur oxidation (Sox) system. This is the first metagenomic study of an acidic, hypersaline depositional environment, and we present evidence for a surprisingly high level of microbial diversity. Our findings also illuminate the possibility that we may be meaningfully underestimating the effects of biology on the chemistry of these sulfur-rich sediments, thereby influencing our understanding of past geobiological conditions that may have been present on Earth as well as early Mars.

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.

The potential for biologically catalyzed anaerobic methane oxidation on ancient Mars.

This study examines the potential for the biologically mediated anaerobic oxidation of methane (AOM) coupled to sulfate reduction on ancient Mars. Seven distinct fluids representative of putative martian groundwater were used to calculate Gibbs energy values in the presence of dissolved methane under a range of atmospheric CO2 partial pressures. In all scenarios, AOM is exergonic, ranging from -31 to -135 kJ/mol CH4. A reaction transport model was constructed to examine how environmentally relevant parameters such as advection velocity, reactant concentrations, and biomass production rate affect the spatial and temporal dependences of AOM reaction rates. Two geologically supported models for ancient martian AOM are presented: a sulfate-rich groundwater with methane produced from serpentinization by-products, and acid-sulfate fluids with methane from basalt alteration. The simulations presented in this study indicate that AOM could have been a feasible metabolism on ancient Mars, and fossil or isotopic evidence of this metabolic pathway may persist beneath the surface and in surface exposures of eroded ancient terrains.

Subsurface water and clay mineral formation during the early history of Mars.

Clay minerals, recently discovered to be widespread in Mars's Noachian terrains, indicate long-duration interaction between water and rock over 3.7 billion years ago. Analysis of how they formed should indicate what environmental conditions prevailed on early Mars. If clays formed near the surface by weathering, as is common on Earth, their presence would indicate past surface conditions warmer and wetter than at present. However, available data instead indicate substantial Martian clay formation by hydrothermal groundwater circulation and a Noachian rock record dominated by evidence of subsurface waters. Cold, arid conditions with only transient surface water may have characterized Mars's surface for over 4 billion years, since the early-Noachian period, and the longest-duration aqueous, potentially habitable environments may have been in the subsurface.

Orbital identification of carbonate-bearing rocks on Mars.

Geochemical models for Mars predict carbonate formation during aqueous alteration. Carbonate-bearing rocks had not previously been detected on Mars' surface, but Mars Reconnaissance Orbiter mapping reveals a regional rock layer with near-infrared spectral characteristics that are consistent with the presence of magnesium carbonate in the Nili Fossae region. The carbonate is closely associated with both phyllosilicate-bearing and olivine-rich rock units and probably formed during the Noachian or early Hesperian era from the alteration of olivine by either hydrothermal fluids or near-surface water. The presence of carbonate as well as accompanying clays suggests that waters were neutral to alkaline at the time of its formation and that acidic weathering, proposed to be characteristic of Hesperian Mars, did not destroy these carbonates and thus did not dominate all aqueous environments.

Phyllosilicate diversity and past aqueous activity revealed at Mawrth Vallis, Mars.

Observations by the Mars Reconnaissance Orbiter/Compact Reconnaissance Imaging Spectrometer for Mars in the Mawrth Vallis region show several phyllosilicate species, indicating a wide range of past aqueous activity. Iron/magnesium (Fe/Mg)-smectite is observed in light-toned outcrops that probably formed via aqueous alteration of basalt of the ancient cratered terrain. This unit is overlain by rocks rich in hydrated silica, montmorillonite, and kaolinite that may have formed via subsequent leaching of Fe and Mg through extended aqueous events or a change in aqueous chemistry. A spectral feature attributed to an Fe2+ phase is present in many locations in the Mawrth Vallis region at the transition from Fe/Mg-smectite to aluminum/silicon (Al/Si)-rich units. Fe2+-bearing materials in terrestrial sediments are typically associated with microorganisms or changes in pH or cations and could be explained here by hydrothermal activity. The stratigraphy of Fe/Mg-smectite overlain by a ferrous phase, hydrated silica, and then Al-phyllosilicates implies a complex aqueous history.

Humans to Mars: a feasibility and cost-benefit analysis.

Mars is a compelling astrobiological target, and a human mission would provide an opportunity to collect immense amounts of scientific data. Exploration alone, however, cannot justify the increased risk. Instead, three factors drive a human mission: economics, education, and exploration. A human mission has a unique potential to inspire the next generation of young people to enter critically needed science and engineering disciplines. A mission is economically feasible, and the research and development program put in place for a human mission would propel growth in related high-technology industries. The main hurdles are human physiological responses to 1-2 years of radiation and microgravity exposure. However, enabling technologies are sufficiently mature in these areas that they can be developed within a few decade timescale. Hence, the decision of whether or not to undertake a human mission to Mars is a political decision, and thus, educational and economic benefits are the crucial factors.