Ancient Siliciclastic-Evaporites as Seen by Remote Sensing Instrumentation with Implications for the Rover-Scale Exploration of Sedimentary Environments on Mars.

Accurate interpretation of the martian sedimentary rock record-and by extension that planet's paleoenvironmental history and potential habitability-relies heavily on rover-based acquisition of textural and compositional data and researchers to properly interpret those data. However, the degree to which this type of remotely sensed information can be unambiguously resolved and accurately linked to geological processes in ancient sedimentary systems warrants further study. In this study, we characterize Mars-relevant siliciclastic-evaporite samples by traditional laboratory-based geological methods (thin section petrography, X-ray diffraction [XRD], backscattered electron imaging, microprobe chemical analyses) and remote sensing methods relevant to martian rover payloads (visible-near-mid infrared reflectance spectroscopy, X-ray fluorescence mapping, XRD). We assess each method's ability to resolve primary and secondary sedimentologic features necessary for the accurate interpretation of paleoenvironmental processes. While the most dominant textures and associated compositions (i.e., bedded gypsum evaporite) of the sample suite are readily identified by a combination of remote sensing techniques, equally important, although more subtle, components (i.e., interbedded windblown silt, meniscus cements) are not resolved unambiguously in bulk samples. However, rover-based techniques capable of coordinating spatially resolved compositional measurements with textural imaging reveal important features not readily detected using traditional assessments (i.e., subtle clay-organic associations, microscale diagenetic nodules). Our findings demonstrate the improved generational capacity of rovers to explore ancient sedimentary environments on Mars while also highlighting the complexities in extracting comprehensive paleoenvironmental information when limited to currently available rover-based techniques. Complete and accurate interpretation of ancient martian sedimentary environments, and by extension the habitability of those environments, likely requires sample return or in situ human exploration. Plain Language Summary Only when correctly translated can the ancient martian sedimentary rock record reveal the environmental evolution of the planet's surface through time. In this case study, we characterize Mars-relevant sedimentary rocks and evaluate the degree to which a comprehensive geological picture can be resolved unambiguously when limited to microscale remote sensing methods relevant to rovers on Mars. While the most dominant textural features and associated compositions of the sample suite are readily identified by a combination of remote sensing techniques, equally important but more subtle components are not resolved unambiguously in bulk samples. However, rover-based techniques capable of coordinating spatially resolved compositional measurements with textural imaging, such as Perseverance Rover's Planetary Instrument for X-Ray Lithochemistry instrument, reveal important features not readily detected by more traditional methods. We demonstrate that rovers have, generationally, improved in their capacity to resolve a true geological picture in ancient sedimentary environments, likely owing to an improved ability to coordinate spatially resolved compositional measurements with textural imaging at the microscale. However, our work also highlights the complexities involved in extracting subtle environmental information when limited to currently available rover-based techniques and suggests that comprehensive interpretation of ancient martian sedimentary systems likely requires sample return or in situ human exploration. Key Points Mars-relevant samples are characterized using both traditional laboratory and microscale rover-based remote sensing techniques to assess each method's ability to recognize features necessary for accurate paleoenvironmental process interpretation. While some key paleoenvironmental processes can reasonably be inferred via remote sensing methods, others cannot be resolved unambiguously. Perseverance Rover's Planetary Instrument for X-Ray Lithochemistry instrument reveals diagenetic features that would otherwise remain unseen by traditional thin section petrography.

Alteration history of Séítah formation rocks inferred by PIXL x-ray fluorescence, x-ray diffraction, and multispectral imaging on Mars.

Collocated crystal sizes and mineral identities are critical for interpreting textural relationships in rocks and testing geological hypotheses, but it has been previously impossible to unambiguously constrain these properties using in situ instruments on Mars rovers. Here, we demonstrate that diffracted and fluoresced x-rays detected by the PIXL instrument (an x-ray fluorescence microscope on the Perseverance rover) provide information about the presence or absence of coherent crystalline domains in various minerals. X-ray analysis and multispectral imaging of rocks from the Séítah formation on the floor of Jezero crater shows that they were emplaced as coarsely crystalline igneous phases. Olivine grains were then partially dissolved and filled by finely crystalline or amorphous secondary silicate, carbonate, sulfate, and chloride/oxychlorine minerals. These results support the hypothesis that Séítah formation rocks represent olivine cumulates altered by fluids far from chemical equilibrium at low water-rock ratios.

Olivine Dissolution in Simulated Lung and Gastric Fluid as an Analog to the Behavior of Lunar Particulate Matter Inside the Human Respiratory and Gastrointestinal Systems.

With the Artemis III mission scheduled to land humans on the Moon in 2025, work must be done to understand the hazards lunar dust inhalation would pose to humans. In this study, San Carlos olivine was used as an analog of lunar olivine, a common component of lunar dust. Olivine was dissolved in a flow-through apparatus in both simulated lung fluid and 0.1 M HCl (simulated gastric fluid) over a period of approximately 2 weeks at physiological temperature, 37°C. Effluent samples were collected periodically and analyzed for pH, iron, silicon, and magnesium ion concentrations. The dissolution rate data derived from our measurements allow us to estimate that an inhaled 1.0 µm diameter olivine particle would take approximately 24 years to dissolve in the human lungs and approximately 3 weeks to dissolve in gastric fluid. Results revealed that inhaled olivine particles may generate the toxic chemical, hydroxyl radical, for up to 5-6 days in lung fluid. Olivine dissolved in 0.1 M HCl for 2 weeks transformed to an amorphous silica-rich solid plus the ferric iron oxy-hydroxide ferrihydrite. Olivine dissolved in simulated lung fluid shows no detectable change in composition or crystallinity. Equilibrium thermodynamic models indicate that olivine in the human lungs can precipitate secondary minerals with fibrous crystal structures that have the potential to induce detrimental health effects similar to asbestos exposure. Our work indicates that inhaled lunar dust containing olivine can settle in the human lungs for years and could induce long-term potential health effects like that of silicosis.

Source-to-Sink Terrestrial Analogs for the Paleoenvironment of Gale Crater, Mars.

In the Late Noachian to Early Hesperian period, rivers transported detritus from igneous source terrains to a downstream lake within Gale crater, creating a stratified stack of fluviolacustrine rocks that is currently exposed along the slopes of Mount Sharp. Controversy exists regarding the paleoclimate that supported overland flow of liquid water at Gale crater, in large part because little is known about how chemical and mineralogical paleoclimate indicators from mafic-rock dominated source-to-sink systems are translated into the rock record. Here, we compile data from basaltic terrains with varying climates on Earth in order to provide a reference frame for the conditions that may have prevailed during the formation of the sedimentary strata in Gale crater, particularly focusing on the Sheepbed and Pahrump Hills members. We calculate the chemical index of alteration for weathering profiles and fluvial sediments to better constrain the relationship between climate and chemical weathering in mafic terrains, a method that best estimates the cooler limit of climate conditions averaged over time. We also compare X-ray diffraction patterns and mineral abundances from fluvial sediments in varying terrestrial climates and martian mudstones to better understand the influence of climate on secondary mineral assemblages in basaltic terrains. We show that the geochemistry and mineralogy of most of the fine-grained sedimentary rocks in Gale crater display first-order similarities with sediments generated in climates that resemble those of present-day Iceland, while other parts of the stratigraphy indicate even colder baseline climate conditions. None of the lithologies examined at Gale crater resemble fluvial sediments or weathering profiles from warm (temperate to tropical) terrestrial climates.

Photogeologic Map of the Perseverance Rover Field Site in Jezero Crater Constructed by the Mars 2020 Science Team.

The Mars 2020 Perseverance rover landing site is located within Jezero crater, a ∼ 50 km diameter impact crater interpreted to be a Noachian-aged lake basin inside the western edge of the Isidis impact structure. Jezero hosts remnants of a fluvial delta, inlet and outlet valleys, and infill deposits containing diverse carbonate, mafic, and hydrated minerals. Prior to the launch of the Mars 2020 mission, members of the Science Team collaborated to produce a photogeologic map of the Perseverance landing site in Jezero crater. Mapping was performed at a 1:5000 digital map scale using a 25 cm/pixel High Resolution Imaging Science Experiment (HiRISE) orthoimage mosaic base map and a 1 m/pixel HiRISE stereo digital terrain model. Mapped bedrock and surficial units were distinguished by differences in relative brightness, tone, topography, surface texture, and apparent roughness. Mapped bedrock units are generally consistent with those identified in previously published mapping efforts, but this study's map includes the distribution of surficial deposits and sub-units of the Jezero delta at a higher level of detail than previous studies. This study considers four possible unit correlations to explain the relative age relationships of major units within the map area. Unit correlations include previously published interpretations as well as those that consider more complex interfingering relationships and alternative relative age relationships. The photogeologic map presented here is the foundation for scientific hypothesis development and strategic planning for Perseverance's exploration of Jezero crater.

Lunar soil simulants alter macrophage survival and function.

Lunar regolith samples collected during previous Apollo missions were found to contain components that were established to be toxic to humans; however, the health effects due to inhalation of lunar soil as a whole are still unknown. Macrophages residing in the alveolar sacs of the lungs constitute one of the last lines of defense against inhaled particulates before entry into the bloodstream. Here, we examine the macrophage response to lunar simulants that are similar in chemical composition to the lunar regolith. We assess cytotoxicity, cellular morphology, phagocytosis of simulants and expression of inflammatory markers. Overall, the exposure of macrophages to lunar simulants results in moderate cytotoxicity and marked alteration of cell morphology and uptake of the simulants. Interestingly, simulant exposure decreased proinflammatory gene expression, but may induce an anti-inflammatory phenotype in the cells. These results illustrate that although macrophages phagocytose lunar simulants as a protective response, the simulants do induce a degree of macrophage cell death. Our study reveals some toxicity associated with lunar simulants and supports further evaluation of the inhalation of lunar regolith to understand the risks of exposure fully.

Author Correction: Reassessing evidence of life in 3,700-million-year-old rocks of Greenland.

In Extended Data Fig. 1 of this Letter, the map showed the field-work location incorrectly; this figure has been corrected online.

Measurement of OH* Generation by Pulverized Minerals Using Electron Spin Resonance Spectroscopy and Implications for the Reactivity of Planetary Regolith.

Mineral analogs to silicate phases common to planetary regolith, including olivine; the pyroxenes augite and diopside; the plagioclase feldspars labradorite, bytownite, and albite; the Johnson Space Center-1A lunar regolith simulant; as well as quartz (used as a reference), were subjected to mechanical pulverization by laboratory milling for times ranging from 5 to 45 min. Pulverized minerals were then incubated in an aqueous solution containing the free radical spin trapping compound 5,5-Dimethyl-1-Pyrroline-N-Oxide for times ranging from 5 to 30 min. These slurries were then analyzed by Electron Paramagnetic Resonance spectroscopy to quantify the amount of hydroxyl radical (the neutral charge form of the hydroxide ion, denoted as OH*) formed in solution. We find that all tested materials generate an Electron Paramagnetic Resonance spectrum indicating the formation of OH* with concentrations ranging between 0.1 and 1.5 µM. We also find that, in general, mineral pulverization time is inversely correlated to OH* generation, while OH* generation is positively correlated to mineral fluid incubation time for phases that have iron in their nominal chemical formulae, suggesting the possible action of Fenton reaction as a cofactor in increasing the reactivity of these phases. Our results add to a body of literature that indicates that the finely comminuted minerals and rocks present in planetary regolith are capable of generating highly reactive and highly oxidizing radical species in solution. The results provide the foundation for further in vitro and in vivo toxicological studies to evaluate the possible health risks that future explorers visiting the surfaces of planetary bodies may face from these reactive regolith materials.

Reassessing evidence of life in 3,700-million-year-old rocks of Greenland.

The Palaeoarchean supracrustal belts in Greenland contain Earth's oldest rocks and are a prime target in the search for the earliest evidence of life on Earth. However, metamorphism has largely obliterated original rock textures and compositions, posing a challenge to the preservation of biological signatures. A recent study of 3,700-million-year-old rocks of the Isua supracrustal belt in Greenland described a rare zone in which low deformation and a closed metamorphic system allowed preservation of primary sedimentary features, including putative conical and domical stromatolites1 (laminated accretionary structures formed by microbially mediated sedimentation). The morphology, layering, mineralogy, chemistry and geological context of the structures were attributed to the formation of microbial mats in a shallow marine environment by 3,700 million years ago, at the start of Earth's rock record. Here we report new research that shows a non-biological, post-depositional origin for the structures. Three-dimensional analysis of the morphology and orientation of the structures within the context of host rock fabrics, combined with texture-specific analyses of major and trace element chemistry, show that the 'stromatolites' are more plausibly interpreted as part of an assemblage of deformation structures formed in carbonate-altered metasediments long after burial. The investigation of the structures of the Isua supracrustal belt serves as a cautionary tale in the search for signs of past life on Mars, highlighting the importance of three-dimensional, integrated analysis of morphology, rock fabrics and geochemistry at appropriate scales.

Magnetite Authigenesis and the Warming of Early Mars.

The Curiosity rover has documented lacustrine sediments at Gale Crater, but how liquid water became physically stable on the early Martian surface is a matter of significant debate. To constrain the composition of the early Martian atmosphere during sediment deposition, we experimentally investigated the nucleation and growth kinetics of authigenic Fe-minerals in Gale Crater mudstones. Experiments show that pH variations within anoxic basaltic waters trigger a series of mineral transformations that rapidly generate magnetite and H2(aq). Magnetite continues to form through this mechanism despite high PCO2 and supersaturation with respect to Fe-carbonate minerals. Reactive transport simulations that incorporate these experimental data show that groundwater infiltration into a lake equilibrated with a CO2-rich atmosphere can trigger the production of both magnetite and H2(aq) in the mudstones. H2(aq), generated at concentrations that would readily exsolve from solution, is capable of increasing annual mean surface temperatures above freezing in CO2-dominated atmospheres. We therefore suggest that magnetite authigenesis could have provided a short-term feedback for stabilizing liquid water, as well as a principal feedstock for biologically relevant chemical reactions, at the early Martian surface.

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.

Assessing Toxicity and Nuclear and Mitochondrial DNA Damage Caused by Exposure of Mammalian Cells to Lunar Regolith Simulants.

Previous missions to the lunar surface implicated potential dangers of lunar soil. In future explorations, astronauts may spend weeks or months on the Moon, increasing the risk of inhaling lunar dust. In an effort to understand the biological impact of lunar regolith, cell cultures derived from lung or neuronal cells were challenged with lunar soil simulants to assess cell survival and genotoxicity. Lunar soil simulants were capable of causing cell death and DNA damage in neuronal and lung cell lines, and freshly crushed lunar soil simulants were more effective at causing cell death and DNA damage than were simulants as received from the supplier. The ability of the simulants to generate reactive oxygen species in aqueous suspensions was not correlated with their cytotoxic or genotoxic affects. Furthermore, the cytotoxicity was not correlated with the accumulation of detectable DNA lesions. These results determine that lunar soil simulants are, with variable activity, cytotoxic and genotoxic to both neuronal and lung-derived cells in culture.

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.

Automating X-ray Fluorescence Analysis for Rapid Astrobiology Surveys.

UNLABELLED: A new generation of planetary rover instruments, such as PIXL (Planetary Instrument for X-ray Lithochemistry) and SHERLOC (Scanning Habitable Environments with Raman Luminescence for Organics and Chemicals) selected for the Mars 2020 mission rover payload, aim to map mineralogical and elemental composition in situ at microscopic scales. These instruments will produce large spectral cubes with thousands of channels acquired over thousands of spatial locations, a large potential science yield limited mainly by the time required to acquire a measurement after placement. A secondary bottleneck also faces mission planners after downlink; analysts must interpret the complex data products quickly to inform tactical planning for the next command cycle. This study demonstrates operational approaches to overcome these bottlenecks by specialized early-stage science data processing. Onboard, simple real-time systems can perform a basic compositional assessment, recognizing specific features of interest and optimizing sensor integration time to characterize anomalies. On the ground, statistically motivated visualization can make raw uncalibrated data products more interpretable for tactical decision making. Techniques such as manifold dimensionality reduction can help operators comprehend large databases at a glance, identifying trends and anomalies in data. These onboard and ground-side analyses can complement a quantitative interpretation. We evaluate system performance for the case study of PIXL, an X-ray fluorescence spectrometer. Experiments on three representative samples demonstrate improved methods for onboard and ground-side automation and illustrate new astrobiological science capabilities unavailable in previous planetary instruments. KEY WORDS: Dimensionality reduction-Planetary science-Visualization.

An integrated view of the chemistry and mineralogy of martian soils.

The mineralogical and elemental compositions of the martian soil are indicators of chemical and physical weathering processes. Using data from the Mars Exploration Rovers, we show that bright dust deposits on opposite sides of the planet are part of a global unit and not dominated by the composition of local rocks. Dark soil deposits at both sites have similar basaltic mineralogies, and could reflect either a global component or the general similarity in the compositions of the rocks from which they were derived. Increased levels of bromine are consistent with mobilization of soluble salts by thin films of liquid water, but the presence of olivine in analysed soil samples indicates that the extent of aqueous alteration of soils has been limited. Nickel abundances are enhanced at the immediate surface and indicate that the upper few millimetres of soil could contain up to one per cent meteoritic material.

Water alteration of rocks and soils on Mars at the Spirit rover site in Gusev crater.

Gusev crater was selected as the landing site for the Spirit rover because of the possibility that it once held a lake. Thus one of the rover's tasks was to search for evidence of lake sediments. However, the plains at the landing site were found to be covered by a regolith composed of olivine-rich basaltic rock and windblown 'global' dust. The analyses of three rock interiors exposed by the rock abrasion tool showed that they are similar to one another, consistent with having originated from a common lava flow. Here we report the investigation of soils, rock coatings and rock interiors by the Spirit rover from sol (martian day) 1 to sol 156, from its landing site to the base of the Columbia hills. The physical and chemical characteristics of the materials analysed provide evidence for limited but unequivocal interaction between water and the volcanic rocks of the Gusev plains. This evidence includes the softness of rock interiors that contain anomalously high concentrations of sulphur, chlorine and bromine relative to terrestrial basalts and martian meteorites; sulphur, chlorine and ferric iron enrichments in multilayer coatings on the light-toned rock Mazatzal; high bromine concentration in filled vugs and veins within the plains basalts; positive correlations between magnesium, sulphur and other salt components in trench soils; and decoupling of sulphur, chlorine and bromine concentrations in trench soils compared to Gusev surface soils, indicating chemical mobility and separation.