Spectral Background Calibration of Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) Spectrometer Onboard the Perseverance Rover Enables Identification of a Ubiquitous Martian Spectral Component.

The Perseverance rover landed at Jezero crater, Mars, on 18 February 2021, with a payload of scientific instruments to examine Mars' past habitability, look for signs of past life, and process samples for future return to Earth. The instrument payload includes the Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) deep ultraviolet Raman and fluorescence imaging spectrometer designed to detect, characterize, and map the presence of organics and minerals on the Martian surface. Operation and engineering constraints sometimes result in the acquisition of spectra with features near the detection limit. It is therefore important to separate instrumental (background) spectral components and spectral components inherent to Martian surface materials. For SHERLOC, the instrumental background is assessed by collecting spectra in the stowed-arm configuration where the instrument is pointed at the Martian nighttime sky with no surface sample present in its optical path. These measurements reveal weak Raman and fluorescence background spectral signatures as well as charged-coupled device pixels prone to erroneous intensity spikes separate from cosmic rays. We quantitatively describe these features and provide a subtraction procedure to remove the spectral background from surface spectra. By identifying and accounting for the SHERLOC Raman background features within the median Raman spectra of Martian target scans, we find that the undefined silicate spectral feature interpreted to be either amorphous silicate or plagioclase feldspar is ubiquitously found in every Mars target Raman scan collected through Sol 751.

Inorganic interpretation of luminescent materials encountered by the Perseverance rover on Mars.

A major objective of the Mars 2020 mission is to sample rocks in Jezero crater that may preserve organic matter for later return to Earth. Using an ultraviolet Raman and luminescence spectrometer, the Perseverance rover detected luminescence signals with maximal intensities at 330 to 350 nanometers and 270 to 290 nanometers that were initially reported as consistent with organics. Here, we test the alternative hypothesis that the 330- to 350-nanometer and 270- to 290-nanometer luminescence signals trace Ce3+ in phosphate and silicate defects, respectively. By comparing the distributions of luminescence signals with the rover detections of x-ray fluorescence from P2O5 and Si-bearing materials, we show that, while an organic origin is not excluded, the observed luminescence can be explained by purely inorganic materials. These findings highlight the importance of eventual laboratory analyses to detect and characterize organic compounds in the returned samples.

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.

Oxidative alteration of ferrous smectites and implications for the redox evolution of early Mars.

Surface conditions on early Mars were likely anoxic, similar to early Earth, but the timing of the evolution to oxic conditions characteristic of contemporary Mars is unresolved. Ferrous trioctahedral smectites are the thermodynamically predicted products of anoxic basalt weathering, but orbital analyses of Noachian-aged terrains find primarily Fe3+-bearing clay minerals. Rover-based detection of Fe2+-bearing trioctahedral smectites at Gale Crater suggest that ferrous smectites are the unoxidized progenitors of orbitally-detected ferric smectites. To assess this pathway, we conducted ambient-temperature oxidative alteration experiments on four synthetic ferrous smectites having molar Fe/(Mg+Fe) from 1.00 to 0.33. Smectite suspension in air-saturated solutions produced incomplete oxidation (24-38% Fe3+/ΣFe). Additional smectite oxidation occurred upon re-exposure to air-saturated solutions after anoxic hydrothermal recrystallization, which accelerated cation and charge redistribution in the octahedral sheet. Oxidation was accompanied by contraction of the octahedral sheet (d(060) decreased from 1.53-1.56 Å to 1.52 Å), consistent with a shift towards dioctahedral structure. Ferrous smectite oxidation by aqueous hydrogen peroxide solutions resulted in nearly complete Fe2+ oxidation but also led to partial Fe3+ ejection from the structure, producing nanoparticulate hematite. Reflectance spectra of oxidized smectites were characterized by (Fe3+,Mg)2-OH bands at 2.28-2.30 µm, consistent with oxidative formation of dioctahedral nontronite. Accordingly, ferrous smectites are plausible precursors to observed ferric smectites on Mars, and their presence in late-Noachian sedimentary units suggests that anoxic conditions may have persisted on Mars beyond the Noachian.

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 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.

Identification of carbonate-rich outcrops on Mars by the Spirit rover.

Decades of speculation about a warmer, wetter Mars climate in the planet's first billion years postulate a denser CO2-rich atmosphere than at present. Such an atmosphere should have led to the formation of outcrops rich in carbonate minerals, for which evidence has been sparse. Using the Mars Exploration Rover Spirit, we have now identified outcrops rich in magnesium-iron carbonate (16 to 34 weight percent) in the Columbia Hills of Gusev crater. Its composition approximates the average composition of the carbonate globules in martian meteorite ALH 84001. The Gusev carbonate probably precipitated from carbonate-bearing solutions under hydrothermal conditions at near-neutral pH in association with volcanic activity during the Noachian era.

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.

Indication of drier periods on Mars from the chemistry and mineralogy of atmospheric dust.

The ubiquitous atmospheric dust on Mars is well mixed by periodic global dust storms, and such dust carries information about the environment in which it once formed and hence about the history of water on Mars. The Mars Exploration Rovers have permanent magnets to collect atmospheric dust for investigation by instruments on the rovers. Here we report results from Mössbauer spectroscopy and X-ray fluorescence of dust particles captured from the martian atmosphere by the magnets. The dust on the magnets contains magnetite and olivine; this indicates a basaltic origin of the dust and shows that magnetite, not maghemite, is the mineral mainly responsible for the magnetic properties of the dust. Furthermore, the dust on the magnets contains some ferric oxides, probably including nanocrystalline phases, so some alteration or oxidation of the basaltic dust seems to have occurred. The presence of olivine indicates that liquid water did not play a dominant role in the processes that formed the atmospheric dust.