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.

Phosphorus in the Clouds of Venus: Potential for Bioavailability.

Aerosol phase elements such as phosphorus (P), sulfur (S), and metals including iron (Fe) are essential nutrients that could help sustain potential biodiversity in the cloud deck of Venus. While the presence of S and Fe in the venusian cloud deck has been broadly discussed (Zasova et al., 1981; Krasnopolsky, 2012, 2013, 2016, 2017; Markiewicz et al., 2014), less attention has been given to the presence of P in the aerosols and its involvement in the multiphase chemistry of venusian clouds and potential sources of P deposition in the venusian atmosphere. A detailed characterization of phosphorus atmospheric chemistry in the cloud deck of Venus is crucial for understanding its solubility and bioavailability for potential venusian cloud microbiota (Schulze-Makuch et al., 2004; Grinspoon and Bullock, 2007; Limaye et al., 2018). We summarize our current understanding of the presence of P in the clouds of Venus and its role in a hypothetical atmospheric (bio)chemical cycle. The results of the VeGa lander measurements are put into perspective with regard to nutrient limitation for a potential biosphere in venusian clouds. Our work combines the results of the VeGa measurements and focuses on P as an inorganic nutrient component and its potential sources and chemical behavior as part of multiple transformations of atmospheric chemistry. The VeGa data indicate that a plentiful phosphorus layer exists within a layer that reaches into the lower venusian clouds and exceeds minimum P abundances for terrestrial microbial life. Extreme acidification of airborne phases in the atmosphere of Venus may facilitate P solubilization and its bioavailability for a potential ecosystem in venusian clouds. Further sampling and P abundance measurements in the atmosphere of Venus would improve our knowledge of P speciation and facilitate determination of a bioavailable fraction of P detected in venusian clouds. The previous results deserve further experimental and modeling analyses to diminish uncertainties and understand the rates of atmospheric deposition of P and its role in a potential venusian cloud ecosystem.

Uninhabitable and Potentially Habitable Environments on Mars: Evidence from Meteorite ALH 84001.

The martian meteorite ALH 84001 formed before ∼4.0 Ga, so it could have preserved information about habitability on early Mars and habitability since then. ALH 84001 is particularly important as it contains carbonate (and other) minerals that were deposited by liquid water, raising the chance that they may have formed in a habitable environment. Despite vigorous efforts from the scientific community, there is no accepted evidence that ALH 84001 contains traces or markers of ancient martian life-all the purported signs have been shown to be incorrect or ambiguous. However, the meteorite provides evidence for three distinct episodes of potentially habitable environments on early Mars. First is evidence that the meteorite's precursors interacted with clay-rich material, formed approximately at 4.2 Ga. Second is that igneous olivine crystals in ALH 84001 were partially dissolved and removed, presumably by liquid water. Third is, of course, the deposition of the carbonate globules, which occurred at ∼15-25°C and involved near-neutral to alkaline waters. The environments of olivine dissolution and carbonate deposition are not known precisely; hydrothermal and soil environments are current possibilities. By analogies with similar alteration minerals and sequences in the nakhlite martian meteorites and volcanic rocks from Spitzbergen (Norway), a hydrothermal environment is favored. As with the nakhlite alterations, those in ALH 84001 likely formed in a hydrothermal system related to a meteoroid impact event. Following deposition of the carbonates (at 3.95 Ga), ALH 84001 preserves no evidence of habitable environments, that is, interaction with water. The meteorite contains several materials (formed by impact shock at ∼3.9 Ga) that should have reacted readily with water to form hydrous silicates, but there is no evidence any formed.

Present-day volcanism on Venus as evidenced from weathering rates of olivine.

At least some of Venus' lava flows are thought to be <2.5 million years old based on visible to near-infrared (VNIR) emissivity measured by the Venus Express spacecraft. However, the exact ages of these flows are poorly constrained because the rate at which olivine alters at Venus surface conditions, and how that alteration affects VNIR spectra, remains unknown. We obtained VNIR reflectance spectra of natural olivine that was altered and oxidized in the laboratory. We show that olivine becomes coated, within days, with alteration products, primarily hematite (Fe2O3). With increasing alteration, the VNIR 1000-nm absorption, characteristic of olivine, also weakens within days. Our results indicate that lava flows lacking VNIR features due to hematite are no more than several years old. Therefore, Venus is volcanically active now.

Clay mineral diversity and abundance in sedimentary rocks of Gale crater, Mars.

Clay minerals provide indicators of the evolution of aqueous conditions and possible habitats for life on ancient Mars. Analyses by the Mars Science Laboratory rover Curiosity show that ~3.5-billion year (Ga) fluvio-lacustrine mudstones in Gale crater contain up to ~28 weight % (wt %) clay minerals. We demonstrate that the species of clay minerals deduced from x-ray diffraction and evolved gas analysis show a strong paleoenvironmental dependency. While perennial lake mudstones are characterized by Fe-saponite, we find that stratigraphic intervals associated with episodic lake drying contain Al-rich, Fe3+-bearing dioctahedral smectite, with minor (3 wt %) quantities of ferripyrophyllite, interpreted as wind-blown detritus, found in candidate aeolian deposits. Our results suggest that dioctahedral smectite formed via near-surface chemical weathering driven by fluctuations in lake level and atmospheric infiltration, a process leading to the redistribution of nutrients and potentially influencing the cycling of gases that help regulate climate.

Silicic volcanism on Mars evidenced by tridymite in high-SiO2 sedimentary rock at Gale crater.

Tridymite, a low-pressure, high-temperature (>870 °C) SiO2 polymorph, was detected in a drill sample of laminated mudstone (Buckskin) at Marias Pass in Gale crater, Mars, by the Chemistry and Mineralogy X-ray diffraction instrument onboard the Mars Science Laboratory rover Curiosity The tridymitic mudstone has ∼40 wt.% crystalline and ∼60 wt.% X-ray amorphous material and a bulk composition with ∼74 wt.% SiO2 (Alpha Particle X-Ray Spectrometer analysis). Plagioclase (∼17 wt.% of bulk sample), tridymite (∼14 wt.%), sanidine (∼3 wt.%), cation-deficient magnetite (∼3 wt.%), cristobalite (∼2 wt.%), and anhydrite (∼1 wt.%) are the mudstone crystalline minerals. Amorphous material is silica-rich (∼39 wt.% opal-A and/or high-SiO2 glass and opal-CT), volatile-bearing (16 wt.% mixed cation sulfates, phosphates, and chlorides-perchlorates-chlorates), and has minor TiO2 and Fe2O3T oxides (∼5 wt.%). Rietveld refinement yielded a monoclinic structural model for a well-crystalline tridymite, consistent with high formation temperatures. Terrestrial tridymite is commonly associated with silicic volcanism, and detritus from such volcanism in a "Lake Gale" catchment environment can account for Buckskin's tridymite, cristobalite, feldspar, and any residual high-SiO2 glass. These cogenetic detrital phases are possibly sourced from the Gale crater wall/rim/central peak. Opaline silica could form during diagenesis from high-SiO2 glass, as amorphous precipitated silica, or as a residue of acidic leaching in the sediment source region or at Marias Pass. The amorphous mixed-cation salts and oxides and possibly the crystalline magnetite (otherwise detrital) are primary precipitates and/or their diagenesis products derived from multiple infiltrations of aqueous solutions having variable compositions, temperatures, and acidities. Anhydrite is post lithification fracture/vein fill.

Mineralogy, provenance, and diagenesis of a potassic basaltic sandstone on Mars: CheMin X-ray diffraction of the Windjana sample (Kimberley area, Gale Crater).

The Windjana drill sample, a sandstone of the Dillinger member (Kimberley formation, Gale Crater, Mars), was analyzed by CheMin X-ray diffraction (XRD) in the MSL Curiosity rover. From Rietveld refinements of its XRD pattern, Windjana contains the following: sanidine (21% weight, ~Or95); augite (20%); magnetite (12%); pigeonite; olivine; plagioclase; amorphous and smectitic material (~25%); and percent levels of others including ilmenite, fluorapatite, and bassanite. From mass balance on the Alpha Proton X-ray Spectrometer (APXS) chemical analysis, the amorphous material is Fe rich with nearly no other cations-like ferrihydrite. The Windjana sample shows little alteration and was likely cemented by its magnetite and ferrihydrite. From ChemCam Laser-Induced Breakdown Spectrometer (LIBS) chemical analyses, Windjana is representative of the Dillinger and Mount Remarkable members of the Kimberley formation. LIBS data suggest that the Kimberley sediments include at least three chemical components. The most K-rich targets have 5.6% K2O, ~1.8 times that of Windjana, implying a sediment component with >40% sanidine, e.g., a trachyte. A second component is rich in mafic minerals, with little feldspar (like a shergottite). A third component is richer in plagioclase and in Na2O, and is likely to be basaltic. The K-rich sediment component is consistent with APXS and ChemCam observations of K-rich rocks elsewhere in Gale Crater. The source of this sediment component was likely volcanic. The presence of sediment from many igneous sources, in concert with Curiosity's identifications of other igneous materials (e.g., mugearite), implies that the northern rim of Gale Crater exposes a diverse igneous complex, at least as diverse as that found in similar-age terranes on Earth.

The chlorine isotope fingerprint of the lunar magma ocean.

The Moon contains chlorine that is isotopically unlike that of any other body yet studied in the Solar System, an observation that has been interpreted to support traditional models of the formation of a nominally hydrogen-free ("dry") Moon. We have analyzed abundances and isotopic compositions of Cl and H in lunar mare basalts, and find little evidence that anhydrous lava outgassing was important in generating chlorine isotope anomalies, because (37)Cl/(35)Cl ratios are not related to Cl abundance, H abundance, or D/H ratios in a manner consistent with the lava-outgassing hypothesis. Instead, (37)Cl/(35)Cl correlates positively with Cl abundance in apatite, as well as with whole-rock Th abundances and La/Lu ratios, suggesting that the high (37)Cl/(35)Cl in lunar basalts is inherited from urKREEP, the last dregs of the lunar magma ocean. These new data suggest that the high chlorine isotope ratios of lunar basalts result not from the degassing of their lavas but from degassing of the lunar magma ocean early in the Moon's history. Chlorine isotope variability is therefore an indicator of planetary magma ocean degassing, an important stage in the formation of terrestrial planets.

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.

Submicron magnetite grains and carbon compounds in Martian meteorite ALH84001: inorganic, abiotic formation by shock and thermal metamorphism.

Purported biogenic features of the ALH84001 Martian meteorite (the carbonate globules, their submicron magnetite grains, and organic matter) have reasonable inorganic origins, and a comprehensive hypothesis is offered here. The carbonate globules were deposited from hydrothermal water, without biological mediation. Thereafter, ALH84001 was affected by an impact shock event, which raised its temperature nearly instantaneously to 500-700K, and induced iron-rich carbonate in the globules to decompose to magnetite and other minerals. The rapidity of the temperature increase caused magnetite grains to nucleate in abundance; hence individual crystals were very small. Nucleation and growth of magnetite crystals were fastest along edges and faces of the precursor carbonate grains, forcing the magnetite grains to be platy or elongated, including the "truncated hexa-octahedra" shape. ALH84001 had formed at some depth within Mars where the lithostatic pressure was significantly above that of Mars' surface. Also, because the rock was at depth, the impact heat dissipated slowly. During this interval, magnetite crystals approached chemical equilibria with surrounding minerals and gas. Their composition, nearly pure Fe(3)O(4), reflects those of equilibria; elements that substitute into magnetite are either absent from iron-rich carbonate (e.g., Ti, Al, Cr), or partitioned into other minerals during magnetite formation (Mg, Mn). Many microstructural imperfections in the magnetite grains would have annealed out as the rock cooled. In this post-shock thermal regime, carbon-bearing gas from the decomposition of iron carbonates reacted with water in the rock (or from its surroundings) to produce organic matter via Fischer-Tropschlike reactions. Formation of such organic compounds like polycyclic aromatic hydrocarbons would have been catalyzed by the magnetite (formation of graphite, the thermochemically stable phase, would be kinetically hindered).