Terrestrial lava tubes serve as analogs for potentially habitable subsurface environments on Mars due to the bioenergetic potential of basalts, formation of secondary minerals, presence of actively seeping fluids, and isolation from the surface. On Earth, a wide variety of microbial communities that thrive in lava tubes often leave behind detectable traces of their presence and activity. To further an understanding of the contribution that secondary minerals, such as amorphous silica, can make to the preservation of organic material in lava tubes, we analyzed a small set of silica-rich basaltic lava tube samples from Mauna Loa, Hawai'i, and Lava Beds National Monument, CA. We applied techniques relevant to current Mars missions (Raman spectroscopy, powder X-ray diffractometry, gas chromatograph-mass spectrometry, scanning electron microscopy, and energy-dispersive X-ray spectrometry) and compared our datasets with those collected previously from similar analyses of siliceous sinter deposits from Yellowstone National Park. Despite variations in major elemental and organic compositions, distributions, and concentrations, we did not observe differences in the Raman spectroscopy and X-ray diffractometer data of the different silica-rich samples. Organic molecules were detected by Raman spectroscopy in all samples with varying degrees of specificity, regardless of the presence of morphological evidence of microbes or apparent degree of silicification. Pyrolysis and thermochemolysis gas chromatograph-mass spectrometry analysis also revealed the presence of numerous organic fragments that were likely derived from the remains of microbial communities in the lava tube samples. Where microbial material was observed, there were often overlapping spectra in some of the biomolecular and amorphous silica Raman signatures, which required careful interpretation that included scanning electron microscopy and gas chromatograph-mass spectrometry. Our data indicate that amorphous silica formation in lava tubes can obscure over time the distinctive morphological characteristics of microbial remains, though the chemical signatures of biomolecular compounds can still be detectable. Our findings have implications for the types of instrument packages that could be selected to assess the chemical makeup and textures of silica-rich lava tube deposits and suggest that more targeted studies are warranted to understand the possible implications for biosignature preservation and detection in such environments.

The ancient climate of Mars changed from warm to cold surface conditions. This climate transition is demonstrated by geomorphological evidence but lacks suitable mineralogical indicators. We investigated the crystallographic properties of hematite (iron oxide) in Gale crater measured by the Curiosity rover and compared them with laboratory experiments. Hematite crystallite sizes are about 5 to 65 nm in the oldest sedimentary rocks investigated by the rover (the Murray formation) and less than 10 nm in the younger overlying strata (the Mirador and Carolyn Shoemaker formations). We attribute the larger crystallites in the Murray formation to postdepositional coarsening by groundwater in warm and wet conditions that persisted for several million years. Hematite with small crystallites co-occurs with goethite (iron oxyhydroxide) in the overlying layers, consistent with colder and water-limited conditions.

Mars has been exposed to ionizing radiation for several billion years, and as part of the search for life on the Red Planet, it is crucial to understand the impact of radiation on biosignature preservation. Several NASA and ESA missions are looking for evidence of ancient life in samples collected at depths shallow enough that they have been impacted by galactic cosmic rays (GCRs). In this study, we exposed a diverse set of Mars analog samples to 0.9 Megagray (MGy) of gamma radiation to mimic 15 million years of exposure on the Martian surface. We measured no significant impact of GCRs on the total organic carbon (TOC) and bulk stable C isotopes in samples with initial TOC concentration > 0.1 wt. %; however, diagnostic molecular biosignatures presented a wide range of degradation that didn't correlate to factors like mineralogy, TOC, water content, and surface area. Exposure dating suggests that the surface of Gale crater has been irradiated at more than five times our dose, yet using this relatively low dose and "best-case scenario" geologically recalcitrant biomarkers, large and variable losses were nevertheless evident. Our results empasize the importance of selecting sampling sites at depth or recently exposed at the Martian surface.

For more than a decade, the CheMin X-ray diffraction instrument on the Mars Science Laboratory rover, Curiosity, has been returning definitive and quantitative mineralogical and mineral–chemistry data from ~3.5-billion-year-old (Ga) sediments in Gale crater, Mars. To date, 40 drilled rock samples and three scooped soil samples have been analyzed during the rover’s 30+ km transit. These samples document the mineralogy of over 800 m of flat-lying fluvial, lacustrine, and aeolian sedimentary rocks that comprise the lower strata of the central mound of Gale crater (Aeolis Mons, informally known as Mt. Sharp) and the surrounding plains (Aeolis Palus, informally known as the Bradbury Rise). The principal mineralogy of the sedimentary rocks is of basaltic composition, with evidence of post-depositional diagenetic overprinting. The rocks in many cases preserve much of their primary mineralogy and sedimentary features, suggesting that they were never strongly heated or deformed. Using aeolian soil composition as a proxy for the composition of the deposited and lithified sediment, it appears that, in many cases, the diagenetic changes observed are principally isochemical. Exceptions to this trend include secondary nodules, calcium sulfate veining, and rare Si-rich alteration halos. A surprising and yet poorly understood observation is that nearly all of the ~3.5 Ga sedimentary rocks analyzed to date contain 15–70 wt.% of X-ray amorphous material. Overall, this >800 m section of sedimentary rock explored in lower Mt. Sharp documents a perennial shallow lake environment grading upward into alternating lacustrine/fluvial and aeolian environments, many of which would have been habitable to microbial life.

Gypsum is a common mineral at Gale crater on Mars, currently being explored by the Mars Science Laboratory (MSL) rover, Curiosity. In this paper, we summarize the associations of gypsum with other sulfate minerals (bassanite, anhydrite, jarosite, starkeyite, and kieserite) from the lowest levels of the crater’s northern moat zone (Aeolis Palus) up through ~0.8 km of the stratigraphic section in the lower slopes of the sedimentary mound developed around the central peak, Aeolis Mons (informally, Mount Sharp). The analysis is based on results from the CheMin X-ray diffraction instrument on Curiosity, supplemented with information from the rover’s versatile instrument suite. Gypsum does not occur with the same frequency as less hydrous Ca-sulfates, likely, in most cases, because of its dehydration to bassanite and possibly to anhydrite. All three of these Ca-sulfate phases often occur together and, along with other sulfates, in mixed assemblages that are evidence of limited equilibration on a cold, dry planet. In almost all samples, at least one of the Ca-sulfate minerals is present, except for a very limited interval where jarosite is the major sulfate mineral, with the implication of more acidic groundwater at a much later time in Gale crater’s history. Although observations from orbit reveal a sulfate-rich surface, currently active dark basaltic dunes at Gale crater have only small amounts of a single sulfate mineral, anhydrite. Gale crater has provided the most complete mineralogical analysis of a site on Mars so far, but the data in hand show that Gale crater mineralogy is not a blueprint with planet-wide application. The concurrent study of Jezero crater by the Mars 2020 mission and comparisons to what is believed to be the most extensive deposit of gypsum on Mars, in the dune fields at the north polar ice cap, show significant diversity. Unraveling the stories of gypsum and other sulfates on Mars is just beginning.

The phyllosilicate-bearing martian plain, Oxia Planum, is the proposed landing site for the Rosalind Franklin rover mission, scheduled to launch in 2028. Rosalind Franklin which will search for signs of past or present life on Mars. Terrestrial analogue sites and simulants can be used to test instruments analogous to those on Rosalind Franklin, however no simulant for Oxia Planum currently exists. In anticipation of this mission, a simulant - SOPHIA (Simulant for Oxia Planum: Hydrated, Igneous, and Amorphous) - representative of the local mineralogy at Oxia Planum has been developed for biosignature and mineralogy experiments, which will assist in interpreting data returned by the rover. The simulant is derived from orbital observations of Oxia Planum and its catchment area. As no in situ data is available for Oxia Planum, mineralogy from other comparable sites on Mars was used to design the simulant including orbital data from Arabia Terra and Mawrth Vallis and in situ data collected from Gale crater. The mineralogy, chemistry and physical properties of the simulant were characterised using standard laboratory techniques (SEM-EDS, XRF, XRD).Techniques analogous to rover instruments (Raman spectroscopy, Near-IR spectroscopy analogous to the Raman laser spectrometer and ISEM and MicrOmega instruments) were also used. The simulant is rich in Fe/Mg phyllosilicates with additional primary igneous and other alteration minerals and is an appropriate spectral and mineralogical analogue for Oxia Planum.

For the first time on Mars, the crystalline magnesium‐sulfate mineral starkeyite (MgSO 4 ‧4H 2 O) was definitively identified using the CheMin X‐ray diffraction instrument at Gale crater. At the Canaima drill site, starkeyite along with amorphous MgSO 4 ‧ n H 2 O are among the “polyhydrated Mg‐sulfates” interpreted in orbital reflectance spectra. Mg‐sulfates are good climate indicators as they are very responsive to changes in temperature and relative humidity. We hypothesize that, through evaporation, Mg‐sulfates formed at the end of brine evolution when ion concentrations became saturated and precipitated on the surface or near sub‐surface as either epsomite or meridianiite. These minerals were subsequently dehydrated later to starkeyite and amorphous MgSO 4 ‧ n H 2 O in response to a drier Mars. At Canaima, starkeyite is stable and would form during the warmer Mars summers. Due to very slow kinetics at the low Mars winter temperatures, starkeyite and amorphous MgSO 4 ‧ n H 2 O would be resistant to recrystallize to more hydrous forms and thus likely persist year‐round. During the course of analyses, starkeyite transforms into amorphous MgSO 4 ‧ n H 2 O inside the rover body due to the elevated temperature and greatly reduced relative humidity compared to the martian surface at the Canaima drill site. It is possible that crystalline sulfate minerals existed in earlier samples measured by CheMin but altered inside the rover before they could be analyzed. Starkeyite is most likely prevalent in the subsurface, whereas both starkeyite and amorphous MgSO 4 ‧ n H 2 O are likely present on the surface as starkeyite could partially transform into amorphous MgSO 4 ‧ n H 2 O due to direct solar heating.

Life detection in the solar system relies on the unambiguous identification of signatures of life and habitability. Organic molecules are essential to life as we know it, and yet many organic compounds are ubiquitous in the solar system and can be synthesized abiotically; thus, their presence alone is not indicative of life. On Earth, chemical signatures of life's processes are often left behind in minerals through the biologically induced formation of secondary minerals or intermediary organic complexes. In natural rocks biomolecules and organic species often co-occur with minerals, and their overlapping peaks can create difficulties in interpretation. In the process of identifying the minerals and organic species in our basaltic samples we noticed signatures for cyanates co-occurring with organic molecules. Cyanates are an overlooked group of nitrogen compounds in which C is bonded to N (e.g., OCN− or SCN−) that often co-occur with urea and ammonium in environments where microorganisms are present. These compounds are common in many terrestrial and oceanic environments and play an important role in biogeochemical nitrogen cycling. In natural systems, these compounds form as the result of multiple biogeochemical pathways, often from the interaction of microbes with a chemically active environment. These interactions leave behind signatures in the form biotic breakdown products such as urea or ammonium and organic reaction byproducts that are observable with spectroscopic methods. To explore these relationships, we used field-portable Raman spectrometers and laboratory micro-Raman imaging to characterize and compare samples collected from two different terrestrial basaltic environments, a lava tube on Mauna Loa, Hawaii, dominated by the precipitation of sulfate minerals and a geothermal stream at Hveragil, Iceland dominated by the precipitation of carbonate minerals. The Raman (RS) measurements were complemented by laser induced breakdown spectroscopy (LIBS), Long-wave Infrared (IR) LIBS, with the addition of gas chromatograph mass spectrometry (GC–MS) and inductively coupled plasma-mass spectrometry (ICP-MS) to identify cyanate compounds, biomolecules, and other nitrogenous compounds related to the breakdown or production of cyanate in host basalts and secondary precipitates. The RS data suggest that the reason for RS cyanate signatures in the carbonate samples could be due to luminescence artifacts while those detected in the host basalts may be due to hydrolysis chemistry. The cyanate signatures detected in the lava tube samples dominated by sulfates do not seem to be luminescence artifacts but may in fact be evidence of an active microbial nitrogen cycle. Our results inform the spectroscopic detection of cyanates in planetary analog environments and the challenges in their identification. Further work is needed to understand their potential as biosignatures on other planetary bodies.

Lava tubes are key targets in the search for life on Mars. Their basaltic walls provide protection from radiation and changing environmental conditions, which could enable life or preservation of previous life in an otherwise harsh environment. We can understand the potential for Martian life in lava tubes by studying the habitability of analog environments on Earth. In this study, we present the first characterization of the microbial life inside a pristine Mauna Loa lava tube. This study is the first to combine 16S SSU rRNA sequencing and whole genome shotgun sequencing to map the taxonomic makeup and functional potential of any lava tube community in Hawaii, enabling a deep understanding of the types of microbes that thrive in this unique environment and the metabolisms they use. We find a surprisingly high degree of niche partitioning over small spatial scales and discuss implications for life detection strategies. Based on recent bioinformatic advancements in metagenomics, we also assemble dozens of high-quality metagenome assembled genomes from the microbes living in the lava tubes, including several novel species.

As we look for traces of ancient life on Mars, we need to consider the impact of ionizing radiation in the biosignature preservation process. Here, we irradiated two organic rich terrestrial samples (Enspel and Messel shales) that have Martian analog mineralogies, with simulated cosmic rays to a dose of 0.9 MGy, equivalent of 15 million years of radiation exposure on the Martian surface. We compared a range of biosignatures before and after exposure, including total organic carbon, bulk stable carbon isotope ratios, diagnostic lipid biomarkers (hopanes and steranes), and Raman signatures akin to those collected by the Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) instrument on Perseverance. While we did not observe a significant difference in total organic carbon, bulk stable carbon isotopes, or Raman G-band signatures, we found that five lipid biomarkers decreased by a factor of two to three in the Enspel shale. This degree of degradation exceeds current predictions by existing models or experimental studies in organic rich samples and challenges our current understanding of complex biosignatures under ionizing irradiation.

The Glen Torridon (GT) region in Gale crater, Mars is a region with strong clay mineral signatures inferred from orbital spectroscopy. The CheMin X‐ray diffraction (XRD) instrument onboard the Mars Science Laboratory rover, Curiosity , measured some of the highest clay mineral abundances to date within GT, complementing the orbital detections. GT may also be unique because in the XRD patterns of some samples, CheMin identified new phases, including: (a) Fe‐carbonates, and (b) a phase with a novel peak at 9.2 Å. Fe‐carbonates have been previously suggested from other instruments onboard, but this is the first definitive reporting by CheMin of Fe‐carbonate. This new phase with a 9.2 Å reflection has never been observed in Gale crater and may be a new mineral for Mars, but discrete identification still remains enigmatic because no single phase on Earth is able to account for all of the GT mineralogical, geochemical, and sedimentological constraints. Here, we modeled XRD profiles and propose an interstratified clay mineral, specifically greenalite‐minnesotaite, as a reasonable candidate. The coexistence of Fe‐carbonate and Fe‐rich clay minerals in the GT samples supports a conceptual model of a lacustrine groundwater mixing environment. Groundwater interaction with percolating lake waters in the sediments is common in terrestrial lacustrine settings, and the diffusion of two distinct water bodies within the subsurface can create a geochemical gradient and unique mineral front in the sediments. Ultimately, the proximity to this mixing zone may have controlled the secondary minerals preserved in sedimentary rocks exposed in GT.

The Curiosity rover in Gale crater is investigating a mineral transition observed from orbit—an older “clay unit” to a younger “sulfate unit”—hypothesized to reflect the aridification of Mars' climate. Below this transition, the rover detected crystalline Ca‐sulfates with minor Fe‐sulfates but also found that some fraction of a rock's bulk SO 3 is often in the poorly constrained X‐ray amorphous component. Here, we characterize the abundances and compositions of the X‐ray amorphous sulfur‐bearing phases in 19 drilled samples using a mass balance approach, and in a subset of 5 samples using evolved SO 2 gas measured using the SAM instrument. We find that ∼20–90 wt% of a sample's bulk SO 3 is in the X‐ray amorphous state and that X‐ray amorphous sulfur‐bearing phase compositions are consistent with mixtures of Mg‐S, Fe‐S, and possibly Ca‐S phases, likely sulfates or sulfites. These phases reside in the bedrock, perhaps as cementing agents deposited with detrital sediments or during early diagenesis, and in diagenetic alteration halos deposited after lithification during late diagenesis. The likely presence of highly soluble Mg‐sulfates in the rocks suggests negligible fluid flow through the bedrock post‐Mg‐sulfate deposition. The X‐ray amorphous sulfur‐bearing phases probably became amorphous through dehydration in the current Martian atmosphere or inside the CheMin instrument. X‐ray amorphous sulfur‐bearing materials likely contribute to orbital spectral detections of sulfates, and so our results help form multiple hypotheses to be tested in the sulfate unit and are important for understanding the evolution of the Martian surface environment at Gale crater.

Evolved gas analysis (EGA) data from the Sample Analysis at Mars (SAM) instrument suite indicated Fe‐rich smectite, carbonate, oxidized organics, Fe/Mg sulfate, and chloride in sedimentary rocks from the Glen Torridon (GT) region of Gale crater that displayed phyllosilicate spectral signatures from orbit. SAM evolved H 2 O data indicated that the primary phyllosilicate in all GT samples was an Fe‐rich dioctahedral smectite (e.g., nontronite) with lesser amounts of a phyllosilicate such as mixed layer talc‐serpentine or greenalite‐minnesotaite. CO 2 data supported the identification of siderite in several samples, and CO 2 and CO data was also consistent with trace oxidized organic compounds such as oxalate salts. SO 2 data indicated trace and/or amorphous Fe sulfates in all samples and one sample may contain Fe sulfides. SO 2 data points to significant Mg sulfates in two samples, and lesser amounts in several other samples. A lack of evolved O 2 indicated the absence of oxychlorine salts and Mn 3+ /Mn 4+ oxides. The lack of, or very minor, evolved NO revealed absent or very trace nitrate/nitrite salts. HCl data suggested chloride salts in GT samples. Constraints from EGA data on mineralogy and chemistry indicated that the environmental history of GT involved alteration with fluids of variable redox potential, chemistry and pH under a range of fluid‐to‐rock ratio conditions. Several of the fluid episodes could have provided habitable environmental conditions and carbon would have been available to any past microbes though the lack of significant N could have been a limiting factor for microbial habitability in the GT region.

We analyze spatially pervasive, light‐toned “halos” associated with fractures in a sedimentary unit (Stimson) of Gale crater, Mars, and report a similar network of halos discovered in a separate geologic group (Bradbury). Through a dedicated active neutron measurement campaign, we provide independent confirmation of the water‐rich nature of these features. Together with mineralogical and geochemical data, these features are consistent with abundant hydrated amorphous silica (opal‐A). We suggest that the mineral and amorphous assemblages are indicative of formation under low‐temperature and predominantly low‐pH conditions (passive silica enrichment) with minor contribution of silica (active silica enrichment) from adjacent units. We show that there is significant amorphous silica in the array of sedimentary rocks in Gale crater, allowing them to play a role in an active silica enrichment phase of halo formation. We suggest that the involved alteration event was short lived and our finding of vast halo networks in a distant, older unit implies a more vast network of hydrologic subsurface conduits than previously known. This relatively recent subsurface hydrologic system was present long after the transition from a warm and wet to a cold and dry Martian environment, extending the habitability conditions on Mars to an epoch that is generally considered not favorable for life on the surface. Finally, our bulk H quantification of these features, which ranges from ∼3–6 wt% H 2 O‐equivalent‐H, suggests that the amorphous material in halos hosts ample supplies of readily released water, making them a considerable resource at the otherwise dry Martian equator.

Aeolian processes have shaped and contributed to the geological record in Gale crater, Mars, long after the fluviolacustrine system existed ∼3 Ga ago. Understanding these aeolian deposits, particularly those which have been lithified and show evidence for aqueous alteration, can help to constrain the environment at their time of deposition and the role of liquid water later in Mars' history. The NASA Curiosity rover investigated a prominent outcrop of aeolian sandstone within the Stimson formation at the Greenheugh pediment as part of its investigation of the Glen Torridon area. In this study, we use geochemical data from ChemCam to constrain the effects of aeolian sedimentary processes, sediment provenance, and diagenesis of the sandstone at the Greenheugh pediment, comparing the Greenheugh data to the results from previous Stimson localities situated 2.5 km north and >200 m lower in elevation. Our results, supported by mineralogical data from CheMin, show that the Stimson formation at the Greenheugh pediment was predominately sourced from an olivine‐rich unit that may be present farther up the slopes of Gale crater's central mound. Our results also suggest that the Greenheugh pediment Stimson formation was cemented by surface water runoff such as that which may have formed Gediz Vallis. The lack of alteration features in the Stimson formation at the Greenheugh pediment relative to those of the Emerson and Naukluft plateaus suggests that groundwater was not as available at this locality compared to the others. However, all sites share diagenesis at the unconformity.

Organic salts, such as Fe, Ca, and Mg oxalates and acetates, may be widespread radiolysis and oxidation products of organic matter in Martian surface sediments. Such organic salts are challenging to identify by evolved gas analysis but the ubiquitous CO2 and CO in pyrolysis data from the Sample Analysis at Mars (SAM) instrument suite on the Curiosity rover indirectly points to their presence. Here, we examined laboratory results from SAM‐like analyses of organic salts as pure phases, as trace phases mixed with silica, and in mixtures with Ca and Mg perchlorates. Pure oxalates evolved CO2 and CO, while pure acetates evolved CO2 and a diverse range of organic products dominated by acetone and acetic acid. Dispersal within silica caused minor peak shifting, decreased the amounts of CO2 evolved by the acetate standards, and altered the relative abundances of the organic products of acetate pyrolysis. The perchlorate salts scrubbed Fe oxalate CO releases and shifted the CO2 peaks to lower temperatures, whereas with Ca and Mg oxalate, a weaker CO release was observed but the initial CO2 evolutions were largely unchanged. The perchlorates induced a stronger CO2 release from acetates at the expense of other products. Oxalates evolved ∼47% more CO2 and acetates yielded ∼69% more CO2 when the perchlorates were abundant. The most compelling fits between our organic salt data and SAM CO2 and CO data included Martian samples acquired from modern eolian deposits and sedimentary rocks with evidence for low‐temperature alteration.

Modified clay minerals on Mars Sedimentary rocks exposed in Gale crater on Mars contain extensive clay minerals. Bristow et al. analyzed drill samples collected by the Curiosity rover as it climbed up sedimentary layers in the crater. They found evidence of past reactions with liquid water and sulfate brines, which could have percolated through the clay from an overlying sulfate deposit. Similar sulfate deposits are widespread across the planet and represent some of the last sedimentary rocks to form before the planet lost its surface liquid water, so the results inform our understanding of the geologic processes that occurred as Mars dried out. Science, abg5449, this issue p. 198

The Mars Science Laboratory Curiosity rover landed in Gale crater, Mars in August 2012 to study a portion of a kilometers-thick sedimentary sequence with evidence for Fe/Mg smectite and sulfate minerals from orbit to interpret past aqueous environments and habitability. Curiosity has investigated nearly 500 m of stratigraphy, and many of the rocks Curiosity has encountered have been laminated mudstones interpreted as lacustrine deposits that were deposited over millions to tens of millions of years. CheMin is an X-ray diffractometer on Curiosity and has analyzed drill powders from 27 ancient fluvio-lacustrine outcrops. CheMin analyses demonstrate changes in type and abundance of igneous silicates, SiO2 phases, phyllosilicates, sulfates, Fe-oxides/oxyhydroxides, and carbonates across Curiosity’s traverse. These changes in mineralogy through the stratigraphic section may be a result of changes in sediment source, lake water chemistry, and diagenetic processes spatially and through time. We will present the mineralogy of the fluvio-lacustrine rocks analyzed by CheMin and evaluate the different hypotheses proposed to explain mineralogical variability.