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The article presents a study of 2020 Perseverance rover's PIXL x-ray fluorescence, x-ray diffraction and multispectral imaging results on Mars to examine the presence or absence of coherent crystalline domains in various minerals. Topics discussed include the capabilities of the PIXL instrument, the formations of the Jezero crater and the Séítah, findings on mineral endmember compositions, and analysis of crystallinity.

The weathering of basalt has implications for the global carbon cycle on Earth as well as for understanding sedimentary processes on other terrestrial bodies dominated by a basaltic crust (e.g., Mars), but yet studies in mafic terrains are limited in comparison to their felsic counterpart. Our work details the compositional transformations resulting from the sedimentation process of first-cycle sediments generated in a basalt dominated watershed of southwest Iceland. By sampling multiple sites along the Hvítá S river transport pathway and analyzing the sedimentology, geochemistry, and mineralogy, this work provides a geologically integrated approach to understanding a fluvial source-to-sink system in mafic terrains. Environmental conditions such as climate, hydrology, and transport distance all influence the overall sediment composition, and in response, chemical weathering, physical abrasion, sorting, transport, and mixing are all sedimentary processes unraveled in the geochemical and mineralogical relationships of individual grain size bins. Chemical weathering initiates in the upper reaches of the watershed with the alteration of primary mafic phases to form secondary weathering products. As sediment continues to move downstream, the entire sediment suite becomes more altered, and the extent of chemical weathering is intensified, as evidenced by a higher abundance of clay minerals and glassy material. Fluvial sorting separates detritus by particle size and differentiates them by compositional gradients in geochemistry and mineralogy. As grain size decreases, mafic minerals become less abundant and the finer grain sizes are preferentially enriched in immature weathering minerals and mineraloids (e.g., smectite clays and X-ray amorphous phases). This grain size trend is also correlated with elemental fractionation, illustrated most notably by the clay size fraction (<2 μm) hosting the most altered material in river sediments. However, we note that the environmental conditions of Iceland (e.g., a cold climate and glacial reworking) result in limited element mobility when compared to more temperate climates around the world. Therefore, we suggest that the clay size fraction of river sediments provide a valuable target for understanding the intensity of weathering in these systems, particularly in a colder climate where mineralogical transformations are not always accompanied by a high degree of elemental loss. In addition to weathering and sorting, trace element abundances suggest the mixing of sediments from varying provenances. While the Hvítá S watershed is dominated by basalt, even minor amounts of evolved volcanics (e.g., andesites) contribute to the overall sediment composition. Overall, this work fills a knowledge gap in sedimentation processes in basaltic terrains on Earth, while additionally providing a valuable terrestrial analog for ancient fluvial-deltaic environments preserved in the sedimentary rock record of Mars (e.g., Gale Crater and Jezero Crater). [ABSTRACT FROM AUTHOR]

Abstract: The nature of ancient hydrological systems on Mars has been the subject of ongoing controversy, driven largely by a disconnect between observational evidence for flowing water on the Martian surface at multiple scales and the incompatibility of such observations with theoretical models that predict a cold early Martian environment in which liquid water is unstable. Here we present geochemical data from the Mars Exploration Rovers to evaluate the hydrological conditions under which weathering rinds, soils, and sedimentary rocks were formed. Our analysis indicates that the chemistry of rinds and soils document a water-limited hydrologic environment where small quantities of S-bearing fluids enter the system, interact with and chemically alter rock and soil, and precipitate secondary mineral phases at the site of alteration with little to no physical separation of primary and secondary mineral phases. In contrast, results show that the sedimentary rocks of the Burns Formation at Meridiani Planum have a chemical composition well-described as a mixture between siliciclastic sediment and sulfate-bearing salts derived from the evaporation of groundwater. We hypothesize that the former may be derived from the recently investigated Shoemaker Formation, a sequence of impact breccias that underlie the Burns Formation. This result has important implications for the style of chemical weathering and hydrology recorded by these sedimentary materials, revealing long-range transport of ions in solution in an open hydrological system that is consistent only with subsurface or overland flow of liquid water. [Copyright &y& Elsevier]

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. [ABSTRACT FROM AUTHOR]

Abstract: The secondary mineral budget on Earth is dominated by clay minerals, Al-hydroxides, and Fe-oxides, which are formed under the moderate pH, high water-to-rock ratio conditions typical of Earth''s near-surface environment. In contrast, geochemical analyses of rocks and soils from landed missions to Mars indicate that secondary mineralogy is dominated by Mg (±Fe, Ca)-sulfates and Fe-oxides. This discrepancy can be explained as resulting from differences in the chemical weathering environment of Earth and Mars. We suggest that chemical weathering processes on Mars are dominated by: (1) a low-pH, sulfuric acid-rich environment in which the stoichiometric dissolution of labile mineral phases such as olivine and apatite (±Fe–Ti oxides) is promoted; and (2) relatively low water-to-rock ratio, such that other silicate phases with slower dissolution rates (e.g., plagioclase, pyroxene) do not contribute substantially to the secondary mineral budget at the Martian surface. Under these conditions, Al-mobilization is limited, and the formation of significant Al-bearing secondary phases (e.g., clays, Al-hydroxides, Al-sulfates) is inhibited. The antiquity of rock samples analyzed in-situ on Mars suggest that water-limited acidic weathering conditions have more than likely been the defining characteristic of the Martian aqueous environment for billions of years. [Copyright &y& Elsevier]

Abstract: Freshly ground basaltic minerals produce sufficient quantities of hydrogen peroxide (H2O2) when immersed in solution to explain the oxidizing characteristics of Martian soil samples collected by the Viking landers. H2O2 production occurs as a result of reactions between water and defects at the surface of mechanically pulverized minerals, analogous to carcinogenic quartz dusts. Our results also indicate that dehydroxylation of mineral surfaces results in increased H2O2 production, a highly relevant finding for dusts on the airless surface of the Moon. Reactive, pulverized minerals are important on planetary bodies where impact processes have generated fine-grained basaltic dusts, and may pose a significant health risk to astronauts visiting planetary surfaces where impacts have generated such materials. [Copyright &y& Elsevier]

The mixed Fe(II)/Fe(III) mineral magnetite [Fe3O4] of various stoichiometric and non‐stoichiometric compositions have been reported in Martian soils and rocks by several rover missions. Magnetite is an important paleomagnetic indicator mineral and can serve as a 'biogeobattery' as a consequence of its magnetic properties and the mixed valence state of iron in its structure. Here, we assess the extent of oxidative weathering of magnetite in presence of chlorate and bromate containing solutions that are likely important oxidants on Mars. Oxyhalogen species, chlorate and bromate, produced non‐stoichiometric magnetite [Fe(II)/Fe(III) < 0.5] in Mars‐relevant, near‐neutral pH fluids; no other ferric minerals were produced. The same results were observed in highly acidic fluids with or without oxyhalogens. Owing to its resistance to extensive oxidation, magnetite can serve as an important archive of geochemical, paleomagnetic, and astrobiological information in samples that will be returned by the Mars Sample Return mission. Plain Language Summary: Magnetite is an iron oxide that contains both Fe(II) and Fe(III) in its crystal structure. The Fe(II) to Fe(III) ratio in an ideal (i.e., stoichiometric) magnetite is 0.5, that decreases as Fe(II) in its structure oxidizes to Fe(III) thereby forming non‐ideal (i.e., non‐stoichiometric) magnetite. Owing to its unique structure, magnetite can serve as an important paleomagnetic indicator mineral and a source of energy for microorganisms. Therefore, understanding the survivability of magnetite in presence of the harsh oxidizing chemical environment on Mars is important. Here, we conduct laboratory experiments in Mars‐like fluids to test the reactivity of magnetite in presence of strong and effective oxidants that have previously been shown to be active on Mars. Our results show that magnetite is resistant to extensive oxidation in presence of chlorate and bromate solutions to an extent that is much greater than other Fe(II) minerals like iron sulfides, and forms non‐stoichiometric magnetite making it a useful target for analyses of samples from the Mars Sample Return mission aimed at understanding Mars' magnetic history and habitability. Key Points: Magnetite shows resistance to oxidation by oxyhalogen compounds (chlorate and bromate) in Mars‐relevant fluidsNon‐stoichiometric magnetite on Mars may be formed by aqueous alteration of stoichiometric magnetite by oxyhalogen compoundsMagnetite likely preserves geochemical, paleomagnetic and astrobiological information and is an important target mineral in Mars return samples [ABSTRACT FROM AUTHOR]

Basaltic sediments generated from the breakdown of the Columbia River Basalts (CRB) in the Lawyer Creek and Lapwai Creek watersheds of northern Idaho demonstrate that sediment composition in these fluvial systems is impacted by a number of processes, including, chemical weathering, sediment mixing, fluvial sorting, and diagenesis. Chemical weathering is documented in the compositional transformations that occur from the parent material to fluvial detritus, specifically in the leaching of labile cations (i.e., Ca, Mg, Na, and K), an overall increase in weathering indices, and the generation of secondary weathering products (i.e., clay minerals and X-ray amorphous phases) in these sediments. While the two watersheds mainly downcut through the Columbia River Basalt, the incorporation of material derived from local, glacially-derived soil and/or second cycle detritus from interbedded sandstone units significantly modifies the chemical and mineralogical signatures that would normally be used to fingerprint a mafic provenance, highlighting a potential difficulty for provenance reconstruction in sedimentary rocks derived from mixed sources. However, the influence of this mixing is less pronounced in the clay size fraction, highlighting the potential of the <2 μm sediments to preserve the chemical weathering history of the provenance during sedimentation. In addition to weathering and mixing, fluvial sorting is also recorded in the sediment composition and results in the separation of weathering products as a function of grain size. This process is first recognized from the enrichment of secondary weathering phases as grain size decreases, thus resulting in the most chemically altered material sorted into the clay size fraction of sediment deposits downstream. Lastly, early diagenesis of fluvial sediments in the CRB watersheds results in a Ce-anomaly that also correlates with grain size, suggesting the preferential formation of oxide phases in the fine-grained fraction. Furthermore, the most positive Ce-anomaly is recorded in an ancient stream deposit, suggesting that authigenic oxide precipitation initiates during sediment accumulation and advances as the deposit is cut off from the active stream channel. [ABSTRACT FROM AUTHOR]

Crewed missions to the Moon may resume as early as 2026 with NASA's Artemis III mission, and lunar dust exposure/inhalation is a potentially serious health hazard that requires detailed study. Current dust exposure limits are based on Apollo‐era samples that spent decades in long‐term storage on Earth; their diminished reactivity may lead to underestimation of potential harm that could be caused by lunar dust exposure. In particular, lunar dust contains nanophase metallic iron grains, produced by "space weathering"; the reactivity of this unique component of lunar dust is not well understood. Herein, we employ a chemical reduction technique that exposes lunar simulants to heat and hydrogen gas to produce metallic iron particles on grain surfaces. We assess the capacity of these reduced lunar simulants to generate hydroxyl radical (OH*) when immersed in deionized (DI) water, simulated lung fluid (SLF), and artificial lysosomal fluid (ALF). Lunar simulant reduction produces surface‐adhered metallic iron "blebs" that resemble nanophase metallic iron particles found in lunar dust grains. Reduced samples generate ~5–100× greater concentrations of the oxidative OH* in DI water versus non‐reduced simulants, which we attribute to metallic iron. SLF and ALF appear to reduce measured OH*. The increase in observed OH* generation for reduced simulants implies high oxidative damage upon exposure to lunar dust. Low levels of OH* measured in SLF and ALF imply potential damage to proteins or quenching of OH* generation, respectively. Reduction of lunar dust simulants provides a quick cost‐effective approach to study dusty materials analogous to authentic lunar dust. [ABSTRACT FROM AUTHOR]

In this work, we studied the x‐ray energy dependence of x‐ray beam diameter focused by polycapillary optics. A quantitative beam diameter–energy relation enables more accurate estimation of the element‐specific interrogation area of a sample using the compositional maps produced by a micro‐XRF system. This improves upon our ability to visualize individual beam‐diameter sized mineral grains and in turn directly benefits Planetary Instrument for X‐ray Lithochemistry (PIXL) analyses of martian soil in addition to benefitting other micro‐focused x‐ray fluorescence (XRF) systems. The spatial distribution of an array of characteristic XRF emission lines was measured by sampling via a knife‐edge approach with small motor stepping of the beam across target edges. Data taken as part of this effort, from the Planetary Flight Model (PFM), were limited to only seven beam energies corresponding to the elements Ni, Cu, Se, Ta, Au, Ti and Ba. Hence, we conducted additional analysis using JPL's lab‐based breadboard (LBB) micro‐XRF system, a system that emulates PIXL's functionality where we measured beam diameter corresponding to 18 elements: Na, Mg, Al, Si, Cl, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, Se, Sr and Mo. The experimental results were also compared with Monte Carlo simulations. The beam diameter (y)–energy (x) relation that we obtained for LBB was y = 185.79 exp(−0.078x) whose exponential component was then used to get a more accurate relation for the PFM even with the limited data set: y = 227.53 exp(−0.078x). The difference in the two coefficients for the PFM and LBB stems mainly from the difference in the polycapillary optic design, and this work establishes x‐ray beam diameter versus energy relation quantitatively for both the systems. [ABSTRACT FROM AUTHOR]

Two decades of intensive research have demonstrated that early Mars (2 Gyr) had an active sedimentary cycle, including well-preserved stratigraphic records, understandable within a source-to-sink framework with remarkable fidelity. This early cycle exhibits first-order similarities to (e.g., facies relationships, groundwater diagenesis, recycling) and first-order differences from (e.g., greater aeolian versus subaqueous processes, basaltic versus granitic provenance, absence of plate tectonics) Earth's record. Mars' sedimentary record preserves evidence for progressive desiccation and oxidation of the surface over time, but simple models for the nature and evolution of paleoenvironments (e.g., acid Mars, early warm and wet versus late cold and dry) have given way to the view that, similar to Earth, different climate regimes on Mars coexisted on regional scales and evolved on variable timescales, and redox chemistry played a pivotal role. A major accomplishment of Mars exploration has been to demonstrate that surface and subsurface sedimentary environments were both habitable and capable of preserving any biological record. ▪ Mars has an ancient sedimentary rock record with many similarities to but also many differences from Earth's sedimentary rock record. ▪ Mars' ancient sedimentary cycle shows a general evolution toward more desiccated and oxidized surficial conditions. ▪ Climatic regimes of early Mars were relatively clement but with regional variations leading to different sedimentary mineral assemblages. ▪ Surface and subsurface sedimentary environments on early Mars were habitable and capable of preserving any biological record that may have existed. [ABSTRACT FROM AUTHOR]

Trace element detection and mapping are key capabilities of the Planetary Instrument for X-ray Lithochemistry (PIXL) on board the Mars 2020 rover Perseverance. However, poor signal-to-noise ratios due to the short integration times required to make high-spatial-resolution map scans operationally feasible raise the possibility of misidentifying statistical noise as a signal from a trace element, which can cause many false detections of a trace element among the hundreds to thousands of data points in each PIXL scan. Here, we apply a statistical technique to quantify the likelihood of such misidentifications and determine what concentration of a trace element must be present to reach statistical confidence in a detection. This approach is anticipated to be applicable both when analyzing existing PIXL data to ensure that noise is not misinterpreted as signals from trace elements and operationally to inform scan parameters when trace elements of interest are anticipated to be present. • M2020 Perseverance PIXL statistical trace element detection confidence is presented • PIXL detection limits for cerium, strontium, and other elements are quantified • Factors influencing trace element detection limits are investigated [ABSTRACT FROM AUTHOR]

We present results from chemostatic siderite precipitation experiments conducted using a modified constant composition method at temperatures between 15 and 75 °C and compare these results with previous temperature relationships to obtain a composite low temperature relationship for siderite clumped isotope ratios (Δ 47) from 8.5 to 75 °C: Δ 47 = 0.0364 ± 0.004 ∗ 10 6 T 2 + 0.1672 ± 0.046 ± 95 % C L , R 2 = 0.708 The slope of this line is statistically indistinguishable from those reported for aragonite, calcite, and dolomite clumped isotopes, but differs in its intercept. To test whether this difference results from mineralogical differences in phosphoric acid fractionation factors (AFF) between siderite and Ca-Mg carbonates, we heated siderite to 625 °C at 1 GPa, which yielded a statistically indistinguishable Δ 47 value from that predicted by published clumped isotope calibrations populated by Ca-and Mg-carbonate data at higher temperatures. Thus, the apparent difference between siderite clumped isotope behavior and that of other carbonate minerals may not be well explained by differences in AFF. Despite differences in precipitation methods, our results are entirely consistent with published inorganic and microbially-mediated experimental siderite clumped isotope data, suggesting that siderite Δ 47 -temperature dependence differs from Ca-Mg carbonates for reasons unrelated to precipitation methods. Our isotopic results are also consistent with published isotopic measurements on natural siderites precipitated at known environmental temperatures. Our analysis leads us to conclude that supersaturation-related kinetic effects likely play an important role in clumped isotope fractionation in natural and experimentally precipitated siderite. [ABSTRACT FROM AUTHOR]

• Gunflint Formation petrography, geochemistry, δ13C, δ18O, and clumped isotopes. • Siderite formed from dissimilatory iron reduction at temperatures as low as 40 °C. • Ferrodolomite-ankerite formed from seawater during burial at elevated temperatures. • Seawater T, δ18O constrained to values of 5–35 °C and −1.0 to −6.5‰, respectively. • Outcrop and core differ because of siderite removal during exposure and weathering. Petrographic, geochemical, C-, O-, and clumped isotope measurements of drill core samples from the Paleoproterozoic (1.88 Ga) Gunflint Iron Formation containing siderite, ankerite, Fe-silicate clays (dominantly greenalite) and silica, reveal variable but light carbonate δ13C values (-21.3 to -7.87‰, VPDB), with heavy and less variable carbonate δ18O values (20.6 to 24.9‰, VSMOW). These measurements are consistent with a model in which siderite is formed during early diagenesis as a by-product of the metabolism of dissimilatory iron reducing (DIR) microbes that consume Fe(III)-oxide and organic carbon delivered from the water column to the sediment-water interface. This model indicates that the oxygen isotope compositions of reactant Fe-oxide, organic matter and dissolved inorganic carbon were set in equilibrium with seawater at T = 5–35 °C and δ18O = -1.0 to -6.5‰, prior to being metabolized to form siderite. Clumped isotope measurements on Fe-bearing carbonates yield temperatures (T(Δ 47)) between 40 °C-132 °C, which constrain δ18O fluid to values between -6.22 to 7.32‰. These measurements record the onset temperature of DIR followed by low water-to-rock ratio diagenetic recrystallization at elevated temperature. Combined petrographic, chemical, and isotopic measurements reveal that the major phases delivered to the shallow seafloor were a disequilibrium assemblage of Fe-oxide, greenalite, silica, and organic matter that underwent microbially mediated modification to form an assemblage of siderite, greenalite, silica, and later diagenetic ankerite. We contend that observed differences between carbonate derived from Gunflint core and outcrop may be reconciled by removal of siderite during exposure and weathering, leaving outcrop enriched in late diagenetic ankerite. [ABSTRACT FROM AUTHOR]

A Correction to this paper has been published: https://doi.org/10.1007/s11214-021-00801-2 [ABSTRACT FROM AUTHOR]

Planetary Instrument for X-ray Lithochemistry (PIXL) is a micro-focus X-ray fluorescence spectrometer mounted on the robotic arm of NASA’s Perseverance rover. PIXL will acquire high spatial resolution observations of rock and soil chemistry, rapidly analyzing the elemental chemistry of a target surface. In 10 seconds, PIXL can use its powerful 120 μm-diameter X-ray beam to analyze a single, sand-sized grain with enough sensitivity to detect major and minor rock-forming elements, as well as many trace elements. Over a period of several hours, PIXL can autonomously raster-scan an area of the rock surface and acquire a hyperspectral map comprised of several thousand individual measured points. When correlated to a visual image acquired by PIXL’s camera, these maps reveal the distribution and abundance variations of chemical elements making up the rock, tied accurately to the physical texture and structure of the rock, at a scale comparable to a 10X magnifying geological hand lens. The many thousands of spectra in these postage stamp-sized elemental maps may be analyzed individually or summed together to create a bulk rock analysis, or subsets of spectra may be summed, quantified, analyzed, and compared using PIXLISE data analysis software. This hand lens-scale view of the petrology and geochemistry of materials at the Perseverance landing site will provide a valuable link between the larger, centimeter- to meter-scale observations by Mastcam-Z, RIMFAX and Supercam, and the much smaller (micron-scale) measurements that would be made on returned samples in terrestrial laboratories. [ABSTRACT FROM AUTHOR]

Recent robotic missions to Mars have offered new insights into the extent, diversity and habitability of the Martian sedimentary rock record. Since the Curiosity rover landed in Gale crater in August 2012, the Mars Science Laboratory Science Team has explored the origins and habitability of ancient fluvial, deltaic, lacustrine and aeolian deposits preserved within the crater. This study describes the sedimentology of a ca 13 m thick succession named the Pahrump Hills member of the Murray formation, the first thick fine‐grained deposit discovered in situ on Mars. This work evaluates the depositional processes responsible for its formation and reconstructs its palaeoenvironmental setting. The Pahrump Hills succession can be sub‐divided into four distinct sedimentary facies: (i) thinly laminated mudstone; (ii) low‐angle cross‐stratified mudstone; (iii) cross‐stratified sandstone; and (iv) thickly laminated mudstone–sandstone. The very fine grain size of the mudstone facies and abundant millimetre‐scale and sub‐millimetre‐scale laminations exhibiting quasi‐uniform thickness throughout the Pahrump Hills succession are most consistent with lacustrine deposition. Low‐angle geometric discordances in the mudstone facies are interpreted as 'scour and drape' structures and suggest the action of currents, such as those associated with hyperpycnal river‐generated plumes plunging into a lake. Observation of an overall upward coarsening in grain size and thickening of laminae throughout the Pahrump Hills succession is consistent with deposition from basinward progradation of a fluvial‐deltaic system derived from the northern crater rim into the Gale crater lake. Palaeohydraulic modelling constrains the salinity of the ancient lake in Gale crater: assuming river sediment concentrations typical of floods on Earth, plunging river plumes and sedimentary structures like those observed at Pahrump Hills would have required lake densities near freshwater to form. The depositional model for the Pahrump Hills member presented here implies the presence of an ancient sustained, habitable freshwater lake in Gale crater for at least ca 103 to 107 Earth years. [ABSTRACT FROM AUTHOR]

Highlights • Curiosity is first robotic drill deployed to another planet since Venera missions. • During first Martian year successfully drilled three full depth drill holes. • Discovered Gale Crater may have once been amenable to Earth-like organisms. • Determined first absolute age date of Martian surface. • Made possible first definitive detection of organic matter on Mars. Abstract The Mars Science Laboratory (MSL) rover, Curiosity, completed its first Martian year, 669 sols (687 Earth days), of operation on June 24, 2014. During that time the rover successfully drilled three full depth drill holes into the Martian surface and analyzed the recovered material using onboard instruments, giving us new insights into the potential habitability of ancient Mars. These drill targets are known as 'John Klein' (Sol 182) and 'Cumberland' (Sol 279), which lie in the mudstones of the Yellowknife Bay formation, and 'Windjana' (Sol 621), which lies in the sandstones of the Kimberley formation. In this paper we will discuss what was necessary to procure these samples, including: 1) an overview of the sampling hardware; 2) the steps taken to ensure sampling hardware is safe when drilling into a target (i.e., evaluation of rock type, rover stability, prior testbed experience, etc.); and 3) the drilling parameters used to acquire these samples. We will also describe each target individually and discuss why each sample was desired, the triage steps taken to ensure it could be safely acquired, and the telemetry obtained for each. Finally, we will present scientific highlights obtained from each site utilizing MSL's onboard instrumentation (SAM & CheMin), results enabled by the drills ability to excavate sample at depth and transfer it to these instruments. [ABSTRACT FROM AUTHOR]

• Oxidation of Fe(II) sulfides by chlorate and bromate studied in Mars-like fluids. • Oxyhalogens highly effective as sulfide oxidants on Mars in diverse fluid systems. • Oxyhalogen brines can explain Amazonian jarosite and amorphous Fe sulfates on Mars. • Sulfide bearing units might be indicators of minimal post-depositional alteration. • Oxyhalogens may be responsible for the loss of magmatic sulfides in Mars sediments. Sulfate salts are abundant, widespread, and temporally distributed on the surface of Mars. Several processes, including sulfide weathering, have been proposed to explain the formation and accumulation of oxidized iron(III) hydroxysulfate (e.g., jarosite) in Martian sediments. Oxidative weathering of iron sulfide minerals (like pyrite and pyrrhotite) could explain the presence of sulfate as well as the relative absence of sulfide minerals in Martian sediments. However, the effectiveness of oxyhalogen compounds, plausible oxidants present on Mars, to weather iron sulfides remain unknown. Here we investigate the oxidative weathering of iron sulfide minerals, pyrite and pyrrhotite, by chlorate and bromate in Mars-relevant fluids. Our results demonstrate that both oxyhalogen species readily oxidize iron sulfides and produce an alteration assemblage comprised of elemental sulfur, Fe(III) (oxyhydr)oxide (magnetite, goethite, and lepidocrocite), and Fe(III) hydroxysulfates (jarosite and schwertmannite). The mineral products depend strongly on the type of sulfide, oxidant, and initial solution pH. Owing to their abundance and highly reactive nature, oxyhalogen brines could be important Fe(III) hydroxysulfate-forming reagents on early and modern Mars and substantially impact the survivability of sulfide minerals at the Martian surface. Additionally, sulfide bearing units might serve as indicators of minimal post-depositional alteration. Oxyhalogens may be responsible for the loss of magmatic sulfides in surface materials given the prevalence of oxyhalogen brines and the reactivity of the sulfides. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

We present a synthesis of PIXL elemental data and SHERLOC Raman spectra collected on two targets investigated by the Perseverance rover during the first year of its exploration of Jezero Crater, Mars. The Bellegarde target (in the Máaz formation) and Dourbes target (in the Séítah formation) exhibit distinctive mineralogies that are an ideal case study for in situ analysis by SHERLOC and PIXL. Each instrument alone produces valuable data about the chemistry and spatial distribution of mineral phases at the sub-millimeter scale. However, combining data from both instruments provides a more robust interpretation that overcomes the limitations of either instrument, for example: 1) Detection of correlated calcium and sulfur in Bellegarde by PIXL is corroborated by the co-located detection of calcium sulfate by SHERLOC. 2) Detection of sodium and chlorine in Dourbes is consistent with either chloride or oxychlorine salts, but SHERLOC does not detect perchlorate or chlorate. 3) A Raman peak at 1120 cm−1 in Dourbes could be sulfate or pyroxene, but elemental abundances from PIXL at that location are a better match to pyroxene. This study emphasizes the importance of analyzing co-located data from both instruments together, to obtain a more complete picture of sub-millimeter-scale mineralogy measured in situ in Jezero crater, Mars, by the Perseverance rover. • The Perseverance rover has two complementary instruments for high-resolution spectral mapping of rocks on Mars • PIXL measures elemental composition, SHERLOC detects chemical composition • Analyzing data from both instruments together allows us to more accurately identify local mineralogy • We use two targets as case studies: Bellegarde (M2az formation)2 and Dourbes (Séítah formation) on the Jezero Crater floor [ABSTRACT FROM AUTHOR]

Silicon stable isotopes are fractionated by a host of low-temperature aqueous processes, making them potentially useful as a weathering proxy. Here we characterize the silicon isotope signature of surficial chemical weathering of glassy basaltic lava flows at Kilauea Volcano, Hawaii. Fresh basalt flow surfaces (<40 years old) frequently feature opaque amorphous silica surface coatings up to 80 μm thick. These silica coatings and associated silica cements are enriched in the heavier isotopes of Si (δ 30 Si NBS-28 = +0.92‰ to +1.36‰) relative to their basaltic substrate (δ 30 Si NBS-28 = −0.3‰ to −0.2‰). Secondary clays and opals are typically depleted in 30 Si relative to the dissolved reservoirs from which they precipitated, so this sense of isotopic fractionation is unusual. Mechanisms capable of producing isotopically heavy secondary minerals were explored by conducting batch alteration experiments on fresh basaltic glass. Batch acidic alteration of basalt glass in HCl, H 2 SO 4 , and HF produced silica-rich surface layers resembling the Hawaiian surface coatings. Differences in fluid chemical composition affected the direction and magnitude of Si isotope fractionation. Basalt leaching in HCl or H 2 SO 4 produced 30 Si-enriched fluids (1000 ln α precip-Si(aq) ≅ −0.8‰) and 30 Si-depleted secondary silica layers. In contrast, HF-bearing experiments produced highly 30 Si-depleted fluid compositions (1000 ln α precip-Si(aq) up to +8‰). Larger isotopic fractionations were observed in experiments with lower fluid–rock ratios. In Hawaii, where altering fluids contain H 2 SO 4 and HCl but minimal HF, high δ 30 Si values for the silica coatings were likely achieved by Rayleigh fractionation. Aqueous 30 Si-enriched silica was released during incongruent basalt dissolution then subsequently transported and deposited from an evaporating solution at the flow surface. Our results indicate that (1) altering fluid chemistry and fluid–rock ratio impact the Si isotope signature of chemical weathering and (2) δ 30 Si of solids produced by low temperature aqueous alteration may diverge sharply from watershed- or landscape-scale weathering trends. [ABSTRACT FROM AUTHOR]

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. Astrobiology 15, 961-976. [ABSTRACT FROM AUTHOR]

Highlights: [•] The Mars Rover Opportunity analyzed Burns Fm ejecta blocks at Santa Maria crater. [•] Many blocks are eolian sandstone, but others are massive, fine-grained and nodular. [•] The fine-grained rocks may be mudstones, formed in a lacustrine setting. [•] This is a unique occurrence of such fine material at Meridiani Planum. [•] Surface water may have created a different environment than previously regarded. [ABSTRACT FROM AUTHOR]

Highlights: [•] Spectral rock classes were found on the rim of Endeavour crater using Pancam multispectral data. [•] Six spectrally unique rock classes were determined. [•] Several of these classes were compared against terrestrial spectral library spectra. [•] Spectral matches were found with pyroxenes, hematite or ferric sulfates, and mineral mixtures. [ABSTRACT FROM AUTHOR]

Abstract: Analysis of visible to near infrared reflectance data from the MRO CRISM hyperspectral imager has revealed the presence of an ovoid-shaped landform, approximately 3 by 5km in size, within the layered terrains surrounding the Mawrth Vallis outflow channel. This feature has spectral absorption features consistent with the presence of the ferric sulfate mineral jarosite, specifically a K-bearing jarosite (KFe3(SO4)2(OH)6). Terrestrial jarosite is formed through the oxidation of iron sulfides in acidic environments or from basaltic precursor minerals with the addition of sulfur. Previously identified phyllosilicates in the Mawrth Vallis layered terrains include a basal sequence of layers containing Fe–Mg smectites and an upper set of layers of hydrated silica and aluminous phyllosilicates. In terms of its fine scale morphology revealed by MRO HiRISE imagery, the jarosite-bearing unit has fracture patterns very similar to that observed in Fe–Mg smectite-bearing layers, but unlike that observed in the Al-bearing phyllosilicate unit. The ovoid-shaped landform is situated in an east–west bowl-shaped depression superposed on a north sloping surface. Spectra of the ovoid-shaped jarosite-bearing landform also display an anomalously high 600nm shoulder, which may be consistent with the presence of goethite and a 1.92μm absorption which could indicate the presence of ferrihydrite. Goethite, jarosite, and ferrihydrite can be co-precipitated and/or form through transformation of schwertmannite, both processes generally occurring under low pH conditions (pH 2–4). To date, this location appears to be unique in the Mawrth Vallis region and could represent precipitation of jarosite in acidic, sulfur-rich ponded water during the waning stages of drying. [Copyright &y& Elsevier]

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. [ABSTRACT FROM AUTHOR]