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Silica Retention and Enrichment in Open-System Chemical Weathering on Mars

Chemical signatures of weathering are evident in the Alpha Particle X-ray Spectrometer (APXS) datasets from Gusev Crater, Meridiani Planum, and Gale Crater. Comparisons across the landing sites show consistent patterns indicating silica retention and/or enrichment in open-system aqueous alteration.

Yen, A. S.↗

Iron-Manganese Redox Reactions in Endeavour Crater Rim Apron Rocks

The Mars Exploration Rover Opportunity has been exploring Noachian age rocks and outcrops on the rim of the 22 km diameter Endeavour crater since August 2011. The Cape York area is a low-lying rim of Endeavour that contains 3 distinct lithologies: 1) the stratigraphically lowest Matijevic fm of pre-impact lithology, 2) Shoemaker fm of impact breccias, and 3) the stratigraphically highest rim lithology Grasberg fm of post-impact sediments that drape the lower slopes of the rim. The sulfate-rich sediment of the Burns fm lies unconformably over the Grasberg fm. Ca-sulfate veins were discovered in Grasberg fm sediments; the sulfates precipitated from aqueous fluids flowing upward through these materials. Opportunity investigated the chemistry and morphology of outcrops in the Matijevic fm that have Fe(sup 3+)-rich smectite detected by orbital signatures returned by CRISM on MRO. Matijevic fm also contains "boxwork" fractures with chemistry consistent with an Al-rich smectite and veins that appear to be rich in Ca-sulfate. More recently on Cape Tribulation, Opportunity has characterized two S-, Mg- and Mn-rich rich rocks overturned and fractured by the rover's wheels on Cook Haven. Those rocks have been dubbed "Pinnacle Island" and "Stuart Island" and will be referred to as the "Island" rocks. The objectives of this study are to characterize the Fe and Mn contents in the Cape York materials, including the two Island rocks, and to provide a model for Mn mobilization and precipitation. Detailed geochemistry of Endeavour rim rocks is presented in a companion paper. Geochemical trends and elemental associations were obtained from data returned by the Alpha Particle X-ray Spectrometer (APXS) on Opportunity.

Ming, D. W.↗

Test and Validation of the Mars Science Laboratory Robotic Arm

The Mars Science Laboratory Robotic Arm (RA) is a key component for achieving the primary scientific goals of the mission. The RA supports sample acquisition by precisely positioning a scoop above loose regolith or accurately preloading a percussive drill on Martian rocks or rover-mounted organic check materials. It assists sample processing by orienting a sample processing unit called CHIMRA through a series of gravity-relative orientations and sample delivery by positioning the sample portion door above an instrument inlet or the observation tray. In addition the RA facilitates contact science by accurately positioning the dust removal tool, Alpha Particle X-Ray Spectrometer (APXS) and the Mars Hand Lens Imager (MAHLI) relative to surface targets. In order to fulfill these seemingly disparate science objectives the RA must satisfy a variety of accuracy and performance requirements. This paper describes the necessary arm requirement specification and the test campaign to demonstrate these requirements were satisfied.

manipulation↗

In-Situ Operations and Planning for the Mars Science Laboratory Robotic Arm: The First 200 Sols

The Robotic Arm (RA) has operated for more than 200 Martian solar days (or sols) since the Mars Science Laboratory rover touched down in Gale Crater on August 5, 2012. During the first seven months on Mars the robotic arm has performed multiple contact science sols including the positioning of the Alpha Particle X-Ray Spectrometer (APXS) and/or Mars Hand Lens Imager (MAHLI) with respect to rocks or loose regolith targets. The RA has supported sample acquisition using both the scoop and drill, sample processing with CHIMRA (Collection and Handling for In- Situ Martian Rock Analysis), and delivery of sample portions to the observation tray, and the SAM (Sample Analysis at Mars) and CHEMIN (Chemistry and Mineralogy) science instruments. This paper describes the planning and execution of robotic arm activities during surface operations, and reviews robotic arm performance results from Mars to date.

Mars surface operations↗

Cementation and Aqueous Alteration of a Sandstone Unit Under Acidic Conditions in Gale Crater, Mars

The Curiosity rover landed on Mars in August 2012 to explore the sedimentary history and to assess the habitability of Gale Crater. After 1200 sols of surface operations and over 12 km of traverse distance, the mineralogy of 10 samples has been determined by the CheMin X-ray diffractometer (XRD) and the chemical composition of nearly 300 targets has been established by the Alpha Particle X-ray Spectrometer (APXS). Light-toned fracture zones containing elevated concentrations of silica have been studied by Curiosity's instruments to determine the nature of the fluids that resulted in the enrichment of SiO2. Multiple fluid exposures are evident, and the chemistry and mineralogy data indicate at least two aqueous episodes may have occurred under acidic conditions.

Yen, A. S.↗

Mineralogical and Geochemical Trends in a Fluviolacustrine Sequence in Gale Crater, Mars

The Mars Science Laboratory rover, Curiosity, landed at Gale crater in August 2012 and has been investigating a sequence of dominantly fluviolacustrine sediments deposited 3.6-3.2 billion years ago. Curiosity collects quantitative mineralogical data with the CheMin XRD/XRF instrument and quantitative chemical data with the APXS and ChemCam instruments. These datasets show stratigraphic mineralogical and geochemical variability that suggest a complex aqueous history. The Murray Formation, primarily composed of fine-laminated mudstone, has been studied in detail since the arrival at the Pahrump Hills in September 2014. CheMin data from four samples show variable amounts of iron oxides, phyllosilicates, sulfates, amorphous and crystalline silica, and mafic silicate minerals. Geochemical data throughout the section show that there is significant variability in Zn, Ni, and Mn concentrations. Mineralogical and geochemical trends with stratigraphy suggest one of possibly several aqueous episodes involved alteration in an open system under acidic pH, though other working hypotheses may explain these and other trends. Data from the Murray Formation contrast with those collected from the Sheepbed mudstone located approximately 60 meters below the base of the Murray Formation, which showed evidence for diagenesis in a closed system at circumneutral pH. Ca-sulfates filled late-stage veins in both mudstones.

Rampe, E.↗

High-Temperature, Perhaps Silicic, Volcanism on Mars Evidenced by Tridymite Detection in High-SiO2 Sedimentary Rock at Gale Crater, Mars

The Mars Science Laboratory (MSL) rover, Curiosity, has been exploring sedimentary rocks within Gale crater since landing in August, 2012. On the lower slopes of Aeolis Mons (a.k.a. Mount Sharp), drill powder was collected from a high-silica (74 wt% SiO2) outcrop named Buckskin (BK). It was a surprise to find that the Buckskin sample contained significant amounts of the relatively rare silica polymorph tridymite. We describe the setting of the Buckskin sample, the detection of tridymite by the MSL Chemistry and Mineralogy (CheMin) X-ray diffraction instrument, and detection implications. Geologic setting: The Buckskin outcrop is part of the Murray formation exposed in the Marias Pass area. The formation was previously studied by CheMin in the Pahrump Hills member [1] where three samples of drill fines were analyzed (Confidence Hills (CH), Mojave2 (MJ) and Telegraph Peak (TP) [2]). Assuming approximately horizontal bedding, the Buckskin outcrop is approx.15 m stratigraphically above the bottom of the Pahrump Hills member. Mudstone, generally characterized by fine lamination, is the dominant depositional facies [1]. Buckskin Mineralogical and Chemical Composition: The CheMin instrument and XRD pattern analysis procedures have been previously discussed [3-6]. The diffraction pattern used for quantitative XRD analysis (Fig. 1) is the sum of the first 4 of 45 diffraction images. The remaining images are all characterized by both on-ring and off-ring diffraction spots that we attributed to poor grain motion and particle clumping. Coincident with particle clumping was a significant decrease in the intensity of the tridymite diffraction peaks (Fig. 2a). The derived mineralogical composition of the crystalline component (derived from the first 4 diffraction images) is given in Table 1. The tridymite is well-crystalline and its pattern is refined as monoclinic tridymite (Fig 1). Mineral chemical compositions were derived from XRD unit cell parameters or obtained from stoichiometry. The XRD-calculated amorphous component was 50 +/- 15 wt%. We constrained the value to 60 wt% because it is the minimum value necessary to give a positive Al2O3 concentration for the amorphous component using APXS data for the post-sieve dump pile (Table 2). The amorphous component has high SiO2 (approx.77 wt%) and high anion (SO3+P2O5+Cl ~10 wt%) concentrations. Calculation shows that a cation-anion balance is achieved if the cations in the amorphous component except SiO2 and TiO2, which do not readily form salts, are assumed to be present as amorphous mixed-cation sulfates, phosphates, and chlorides (or perchlorates/ chlorates).

Morris, R. V.↗

Authigenesis/Diagenesis of the Murray Formation Mudstone in Gale Crater, Mars

The Mars Science Laboratory rover Curiosity has been exploring sedimentary deposits in Gale crater since August, 2012. The rover has traversed up section through approximately 150 m of sedimentary rocks deposited in fluvial, deltaic, and lacustrine environments (Bradbury group and overlying Mount Sharp group). The Murray formation lies at the base of the Mt. Sharp group and has been interpreted to be a finely laminated mudstone likely deposited in a subaqueous lacustrine environment. Four drill samples from several elevations in the Murray fm have been acquired by the rover's sampling system and delivered to the CheMin XRD instrument. The lower section of the Murray fm contains 2:1 phyllosilicate(s), hematite, jarosite, XRD amorphous materials, and primary basaltic minerals. Further up section, the Murray fm contains magnetite, cristobalite, tridymite, abundant Si-rich XRD amorphous materials along with plagioclase and K-feldspars. Murray formation materials appear to have been altered under an open hydrologic system based on the bulk chemistry of these materials measured by the Alpha Particle X-ray Spectrometer (APXS). The 2:1 phyllosilicate only occurs in the lowermost section of the Murray fm and may be detrital or formed during authigenesis of Murray fm materials, similar to the Fe-saponite and magnetite detected in a mudstone in the Yellowknife Bay fm near Curiosity's landing site (stratigraphically at the base of the Bradbury group). The occurrence of jarosite and hematite in the lower section indicates an acidic diagenetic event. These phases may have formed via several acidic alteration mechanisms, including (1) oxidative weathering of mafic igneous rocks containing sulfides; (2) sulfuric acid weathering of Fe-bearing phases; and (3) near-neutral pH subsurface solutions rich in Fe2(+) that were rapidly oxidized to Fe3(+), which produced excess acidity. The transition from abundant hematite in the lowermost Murray fm to magnetite moving up section may indicate changes in lake chemistry, i.e., variable redox conditions, possibly during authigenesis or subsequent diagenetic events. Tridymite, a high temperature mineral, (and possibly cristobalite) is detrital, potentially deposited in a lake from a distal silicic volcanic rock source or from crustal materials present prior to the Gale Crater impact event. Abundant Si-rich XRD amorphous materials in the upper sections of the Murray fm may be detrital or an aqueous alteration product of primary igneous phases and phyllosilicates. Curiosity's science team is still deciphering the authigenesis and diagenetic events that formed the Murray fm. The mineralogy and geochemistry of the formation suggest a complicated history with several (many?) episodes of aqueous alteration under a variety of environmental conditions.

Ming, D. W.↗

Multispectral VNIR Observations by the Opportunity Rover Pancam of Multiple Episodes of Aqueous Alteration in Marathon Valley, Endeavour Crater, Mars

Since early 2015, the Mars Exploration Rover Opportunity has been exploring the break in the rim of Endeavour Crater dubbed Marathon Valley by the rover team. Marathon Valley was identified by orbital hyperspectral data from the MRO CRISM as having a relatively strong spectral feature in the 2.3 micrometer region indicative of an Mg or Fe-OH combination overtone absorption band indicative of smectite clay. Earlier in its mission, Opportunity examined the Matijevic Hill region on the more northerly Cape York crater rim segment and found evidence for smectite clays in a stratigraphically lower, pre-impact formed unit dubbed the Matijevic formation. However, the smectite exposures in Marathon Valley appear to be associated with the stratigraphically higher Shoemaker formation impact breccia. Evidence for alteration in this unit in Marathon Valley is provided by Pancam multispectral observations in the 430 to 1010 nm visible/near infrared (VNIR) spectral range. Sinuous troughs ("red zones") contain fragmented cobbles and pebbles displaying higher blue-to-red slopes, moderately higher 535 nm band depths, elevated 754 to 934 nm, and negative 934 to 1009 nm slopes. The lack of an absorption at 864 to 904 nm indicates the lack of crystalline red hematite in these red zones, but likely an enrichment in nanophase ferric oxides. The negative 934 to 1009 nm slope is potentially indicative of the presence of adsorbed or structurally bound water. A scuff in a red zone near the southern wall of Marathon Valley uncovered light-toned soils and a pebble with an 803 to 864 nm absorption resembling that of light-toned Fe-sulfate bearing soils uncovered by the Spirit rover in the Columbia Hills of Gusev crater. APXS chemical measurements indicated enrichments of Mg and S in the scuff soils and the pebble, Joseph Field, with the strongest 803 nm band- consistent with Mg and Fe sulfates. The presence of Fe and Mg sulfates can be interpreted as evidence of a potentially later episode of aqueous alteration with an earlier, neutral to alkaline pH episode forming the Fe/Mg smectites and a later acid pH episode forming the Fe and Mg sulfates.

Farrand, William H.↗

The Potassium-Argon Laser Experiment (karle): In Situ Geochronology for Planetary Missions

Isotopic dating is an essential tool to establish an absolute chronology for geological events. It enables a planet's crystallization history, magmatic evolution, and alteration to be placed into the framework of solar system history. The capability for in situ geochronology will open up the ability for this crucial measurement to be accomplished as part of lander or rover complement. An in situ geochronology package can also complement sample return missions by identifying the most interesting rocks to cache or return to Earth. Appropriate application of in situ dating will enable geochronology on more terrains than can be reached with sample-return missions to the Moon, Mars, asteroids, outer planetary satellites, and other bodies that contain rocky components. The capability of flight instruments to conduct in situ geochronology is called out in the NASA Planetary Science Decadal Survey and the NASA Technology Roadmap as needing development to serve the community's needs. Beagle 2 is the only mission launched to date with the explicit aim to perform in situ K-Ar isotopic dating [1], but it failed to communicate and was lost. The first in situ K-Ar date on Mars, using SAM and APXS measurements on the Cumberland mudstone [2], yielded an age of 4.21 +/- 0.35 Ga and validated the idea of K-Ar dating on other planets, though the Curiosity method is not purpose-built for dating and requires many assumptions that degrade its precision. To get more precise and meaningful ages, multiple groups are developing dedicated in situ dating instruments.

planetary↗

Acid-Sulfate Alteration at Gusev Crater and Across Mars: High-SiO2 Residues and Ferric Sulfate Precipitates

The Mars Exploration Rover Spirit ended its mission in Gusev crater on sol 2210 after it had become stuck in a deposit of fined-grained and sulfate rich soil with dust covered solar panels unfavorably pointed toward the sun. Final analysis of remaining data from Spirit's Moessbauer spectrometer (Fe redox and mineralogy) for sols 1529 through 2071 is now complete. We focus here on chemical (APXS) and MB data for targets having high-SiO2 or high-SO3 and process link the targets through mixing and geochemical modelling to an acid-sulfate system centered at Home Plate, which is considered to be a hydrovolcanic complex.

Morris, R. V.↗

X-Ray Amorphous Phases in Terrestrial Analog Volcanic Sediments: Implications for Amorphous Phases in Gale Crater, Mars

X-ray diffraction (XRD) amorphous phases have been found as major components (approx.15-60 wt%) of all rock and soil samples measured by the CheMin XRD instrument in Gale Crater, Mars. The nature of these phases is not well understood and could be any combination of primary (e.g., glass) and secondary (e.g., allophane) phases. Amorphous phases form in abundance during surface weathering on Earth. Yet, these materials are poorly characterized, and it is not certain how properties like composition and structure change with formation environment. The presence of poorly crystalline phases can be inferred from XRD patterns by the appearance of a low angle rise (< or approx.10deg 2(theta)) or broad peaks in the background at low to moderate 2(theta) angles (amorphous humps). CheMin mineral abundances combined with bulk chemical composition measurements from the Alpha Particle X-ray Spectrometer (APXS) have been used to estimate the abundance and composition of the XRD amorphous materials in soil and rock samples on Mars. Here we apply a similar approach to a diverse suite of terrestrial samples - modern soils, glacial sediments, and paleosols - in order to determine how formation environment, climate, and diagenesis affect the abundance and composition of X-ray amorphous phases.

Smith, R. J.↗

Constraining the Origin of Basaltic Volcanic Rocks Observed by Opportunity Along the Rim of Endeavour Crater

The Mars Exploration Rover (MER) Opportunity continues its exploration along the rim of Endeavour Crater. While the primary focus for investigation has been to seek evidence of aqueous alteration, Opportunity has observed a variety of rock types, including some that are hard and relatively unaltered. These rocks tend to occur most commonly as "float rocks" or "erratics" where the geologic setting does not clearly reveal their origin. Along the rim of Endeavour crater (Fig. 1), such rocks, commonly noted in Panoramic Camera (Pancam) left eye composites as "blue rocks", are abundant components of some of the Endeavour crater rim deposits, scree slopes, and colluvium deposits. In this abstract, we examine the similarity of several of these rocks analyzed using Opportunity's Alpha Particle X-Ray Spectrometer (APXS), images and color from the Pancam, and textures observed with the Microscopic Imager (MI. At issue is the blue rocks origin; are they impact melt or volcanic, what is their age relative to Endeavour crater, and how they are related to each other?

Bouchard, M. C.↗

Bulk Hydrogen Content OF High-Silica Rocks in Gale Crater With the Active Dynamic Albedo of Neutrons Experiment

The Mars Science Laboratory (MSL) Curiosity rover recently traversed over plateaus of mafic aeolian sandstones (the 'Stimson' formation) that overlie mudstones (the 'Murray' formation). Within the Stimson formation we observed many lighter-toned, halo-forming features, that are potentially indicative of fluid alteration (see Fig. 1). These halo features extend for tens of meters laterally and are approx.1 meter wide. The halo features were characterized by Curiosity's geochemical instruments: Alpha Proton X-Ray Spectrometer (APXS), Chemin, Chemcam and Sample Analysis at Mars (SAM). With respect to the host (unaltered) Stimson rocks, fracture halos were significantly enriched in silicon and low in iron [1]. Changes in hydrogen abundance (due to its large neutron scattering cross section) greatly influence the magnitude of the thermal neutron response from the Dynamic Albedo of Neutrons (DAN) instrument [2]. There are also some elemental species, e.g. chlorine, iron, and nickel, that have significant microscopic neutron absorption cross sections. These elements can be abundant and variable results provide a useful estimate of the lower bound for bulk hydrogen content (assuming a homogeneous distribution).

Gabriel, T. S. J.↗

The Potassium-Argon Laser Experiment (KArLE): Design Concepts

The absolute ages of geologic events are fundamental information for understanding the timing and duration of surface processes on planetary bodies. Absolute ages can place a planet's history in the context of the solar system evolution. For example, "when was Mars warm and wet?" is one of the key questions of planetary science. If Mars was warm and wet until 3.7 billion years ago, for instance, it suggests that Mars was still warm and wet when life appeared on Earth. Mars history has been discussed so far based on crater chronology, but the current constraints for Martian chronology models come from the cratering history of the Moon [1]. Moreover, the lunar chronology model itself is fraught with uncertainty because our understanding of lunar chronology is constrained only in a few time periods and itself needs further investigation relating crater-counting ages to absolute ages [2]. Although sample return missions would provide highly accurate radiometric ages of returned samples, they are very expensive and technically challenging. In situ geochronology is highly valuable because they would have larger number of mission opportunities and the capability of iterative measurements for multiple rocks from multiple geologic units. The capability of flight instruments to perform in situ dating is required in the NASA Planetary Science Decadal Survey and the NASA Technology Roadmap. Beagle 2 is the only mission launched to date with the explicit aim to perform in situ potassium-argon (K-Ar) dating [3], but it did not happen because of the communication failure to the spacecraft. The first in situ K-Ar dating on Mars, using SAM and APXS measurements on the Cumberland mudstone [4], yielded an age of 4.21 +/- 0.35 Ga and validated the idea of K-Ar dating on other planets. However, the Curiosity method is not purposebuilt for dating and requires many assumptions that degrade its accuracy. To obtain more accurate and meaningful ages, multiple groups are developing dedicated in situ dating instruments [5-8].

design↗

Mineralogical Changes in a Predominantly Fluviolacustrine Succession at Gale Crater, Mars

The Mars Science Laboratory Curiosity rover landed in Gale crater in August 2012 to investigate the strata of lower Aeolis Mons (i.e., Mount Sharp) and characterize their depositional and diagenetic environments. Visible/short-wave infrared spectra from orbit of these strata show variations in phyllosilicate, sulfate, and Fe-oxide minerals, suggesting these units record environmental changes that occurred during the early Hesperian. Curiosity has traversed over 15 km and has climbed through Approx. 200 m of stratigraphic section, made up of predominantly fluviolacustrine (i.e., the Bradbury group and the Murray formation) and aeolian (i.e., the Stimson formation) units. Multiple geochemical and mineralogical instruments are onboard Curiosity to study these ancient rocks, including the Chemistry and Mineralogy (CheMin) instrument, which is an X-ray diffractometer (XRD) and X-ray fluorescence spectrometer, and the Alpha Particle X-ray Spectrometer (APXS).

Rampe, E. B.↗

The Contrast in Outgassing of Germanium Between Shergottites and Nakhlites

Final Paper and not the abstract is attached. Introduction: Germanium is generally thought to follow Si in its geochemical behavior, but little data has existed to rigorously understand the behavior of Ge in the Martian mantle. Germanium is known to be more siderophile than Si, and its partitioning into the martian core has been studied by. Typical abundances in igneous martian meteorites range from 0.5-3 ppm, a larger range than what is observed in terrestrial basalts (1.5 +/- 0.1 ppm). In situ measurements by the MER and MSL rovers have revealed a surprisingly large range in Ge abundances in surface rocks (30-650 ppm), but many igneous rocks and soils are shown to have greater than 30 ppm Ge (the detection limit of the APXS). Recently, reported that shergottite minerals showed a depletion of Ge with increasing fractionation, while nakhlites and chassignites exhibited Ge behavior compatible with closed system igneous differentiation. They interpreted their observations as tentatively indicating volcanic outgassing of Ge from shergottites (but not from nakhlite-chassignites) with recondensation of the Ge vapor into soils and breccias. Recent experimental studies show that Ge is significantly volatile from magmas. In this study, we followed up on those results by analyzing minerals in five nakhlites and five shergottites by laser ablation ICP-MS (LA-ICP-MS). See Attached

Yang, S.↗

Amorphous Phase Characterization Through X-Ray Diffraction Profile Modeling: Implications for Amorphous Phases in Gale Crater Rocks and Soils

The CheMin X-ray diffraction instrument on the Mars Science Laboratory rover has analyzed 18 rock and soil samples in Gale crater. Diffraction data allow for the identification of major crystalline phases based on the positions and intensities of well-defined peaks and also provides information regarding amorphous and poorly-ordered materials based on the shape and positions of broad scattering humps. The combination of diffraction data, elemental chemistry from APXS (Alpha Particle X-ray Spectrometer) and evolved gas analyses (EGA) from SAM (Sample Analysis at Mars) help constrain possible amorphous materials present in each sample (e.g., glass, opal, iron oxides, sulfates) but are model dependent. We present a novel method to characterize amorphous material in diffraction data and, through this approach, aim to characterize the phases collectively producing the amorphous profiles in CheMin diffraction data. This method may be applied to any diffraction data from samples containing X-ray amorphous materials, not just CheMin datasets, but we re-strict our discussion to Martian-relevant amorphous phases and diffraction data measured by CheMin or CheMin-like instruments.

Achilles, C. N.↗