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Noachian Impact Breccias on the Rim of Endeavour Crater, Mars: Opportunity APXS Results

Mars Exploration Rover Opportunity has been investigating the geology of Meridiani Planum since January 2004, and is currently approx. 3830% into its primary mission. Opportunity reached the rim of 22 km diameter Endeavor crater at Spirit Point on the south end of Cape York on sol 2681 and began exploring the geology of Endeavour rim. She left Cape York on sol 3316 and arrived at the next rim remnant to the south, Solander Point, on sol 3387 to begin geological investigations at the contact and up onto Murray Ridge. The Burns fm. of Meridiani Planum lies near the top of the plains-forming unit of western Sinus Meridiani and onlaps onto the Endeavour rim rocks (hereafter rim rocks). Endeavour crater would have excavated approx. 4 km into the existing stratigraphy. Thus, the ejecta that form the rim rocks offer windows into the deeper lithologies of Sinus Meridiani. Here we discuss the polymict breccias of the Shoemaker fm. on Cape York and the breccias from Murray Ridge, with a focus on compositions determined by the Alpha Particle X-Ray Spectrometer (APXS).

Mittlefehldt, D. W.↗

Ground Truthing Orbital Clay Mineral Observations with the APXS Onboard Mars Exploration Rover Opportunity

NASA's Mars Exploration Rover Opportunity has been exploring approximately 22 km diameter Endeavour crater since 2011. Its rim segments predate the Hesperian-age Burns formation and expose Noachian-age material, which is associated with orbital Fe3+-Mg-rich clay mineral observations [1,2]. Moving to an orders of magnitude smaller instrumental field of view on the ground, the clay minerals were challenging to pinpoint on the basis of geochemical data because they appear to be the result of near-isochemical weathering of the local bedrock [3,4]. However, the APXS revealed a more complex mineral story as fracture fills and so-called red zones appear to contain more Al-rich clay minerals [5,6], which had not been observed from orbit. These observations are important to constrain clay mineral formation processes. More detail will be added as Opportunity is heading into her 10th extended mission, during which she will investigate Noachian bedrock that predates Endeavour crater, study sedimentary rocks inside Endeavour crater, and explore a fluid-carved gully. ESA's ExoMars rover will land on Noachian-age Oxia Planum where abundant Fe3+-Mg-rich clay minerals have been observed from orbit, but the story will undoubtedly become more complex once seen from the ground.

Schroeder, C.↗

Compositional Characteristics and Trends Within the Vera Rubin Ridge, Gale Crater, Mars as Determined by APXS: Sedimentary, Diagenetic and Alteration History

The Mars Science Laboratory (MSL) Curiosity rover has spent the last two years investigating a prominent resistant ridge, informally named the Vera Rubin Ridge (VRR), at the base of Mount Sharp (Aeolis Mons). The ridge has been a high priority science target for the MSL mission since landing in Gale crater more than 6 years ago because of the detection of a strong hematite spectral signature, and its distinct topography. Examining the chemistry of the ridge can aid in determining the relationship to other rocks analyzed during the rover traverse, specifically the Murray formation (fm) encountered below the ridge. We can also determine compositional trends with elevation and/or laterally within the ridge, and whether spectral properties observed on the ridge, both from orbit and in situ, correspond with changes in chemistry. The composition of the ridge, combined with mineralogy of drilled samples, can help to elucidate bigger picture questions regarding depositional environment, possible changing lake water chemistry and diagenetic/alteration history.

Thompson, L. M.↗

A sorghum ascorbate peroxidase with four binding sites has activity against ascorbate and phenylpropanoids

Abstract In planta, H2O2 is produced as a by-product of enzymatic reactions and during defense responses. Ascorbate peroxidase (APX) is a key enzyme involved in scavenging cytotoxic H2O2. Here, we report the crystal structure of cytosolic APX from sorghum (Sorghum bicolor) (Sobic.001G410200). While the overall structure of SbAPX was similar to that of other APXs, SbAPX uniquely displayed four bound ascorbates rather than one. In addition to the ɣ-heme pocket identified in other APXs, ascorbates were bound at the δ-meso and two solvent-exposed pockets. Consistent with the presence of multiple binding sites, our results indicated that the H2O2-dependent oxidation of ascorbate displayed positive cooperativity. Bound ascorbate at two surface sites established an intricate proton network with ascorbate at the ɣ-heme edge and δ-meso sites. Based on crystal structures, steady-state kinetics, and site-directed mutagenesis results, both ascorbate molecules at the ɣ-heme edge and the one at the surface are expected to participate in the oxidation reaction. We provide evidence that the H2O2-dependent oxidation of ascorbate by APX produces a C2-hydrated bicyclic hemiketal form of dehydroascorbic acid at the ɣ-heme edge, indicating two successive electron transfers from a single-bound ascorbate. In addition, the δ-meso site was shared with several organic compounds, including p-coumaric acid and other phenylpropanoids, for the potential radicalization reaction. Site-directed mutagenesis of the critical residue at the ɣ-heme edge (R172A) only partially reduced polymerization activity. Thus, APX removes stress-generated H2O2 with ascorbates, and also uses this same H2O2 to potentially fortify cell walls via oxidative polymerization of phenylpropanoids in response to stress.

Plant Sciences↗

Automated Grouping of Opportunity Rover Alpha Particle X-Ray Spectrometer Compositional Data

The Alpha Particle X-ray Spectrometer (APXS) conducts high-precision in situ measurements of rocks and soils on both active NASA Mars rovers. Since 2004 the rover Opportunity has acquired around 440 unique APXS measurements, including a wide variety of compositions, during its 42+ kilometers traverse across several geological formations. Here we discuss an analytical comparison algorithm providing a means to cluster samples due to compositional similarity and the resulting automated classification scheme. Due to the inherent variance of elements in the APXS data set, each element has an associated weight that is inversely proportional to the variance. Thus, the more consistent the abundance of an element in the data set, the more it contributes to the classification. All 16 elements standard to the APXS data set are considered. Careful attention is also given to the errors associated with the composition measured by the APXS - larger uncertainties reduce the weighting of the element accordingly. The comparison of two targets, i and j, generates a similarity score, S(sub ij). This score is immediately comparable to an average ratio across all elements if one assumes standard weighted uncertainty. The algorithm facilitates the classification of APXS targets by chemistry alone - independent of target appearance and geological context which can be added later as a consistency check. For the N targets considered, a N by N hollow matrix, S, is generated where S = S(sup T). The average relation score, S(sub av), for target N(sub i) is simply the average of column i of S. A large S(sub av) is indicative of a unique sample. In such an instance any targets with a low comparison score can be classified alike. The threshold between classes requires careful consideration. Applying the algorithm to recent Marathon Valley targets indicates similarities with Burns formation and average-Mars-like rocks encountered earlier at Endeavour Crater as well as a new class of felsic rocks.

VanBommel, S. J.↗

Two Years of Chemical Sampling on Meridiani Planum by the Alpha Particle X-Ray Spectrometer Onboard the Mars Exploration Rover Opportunity

For over two terrestrial years, the Mars Exploration Rover Opportunity has been exploring the martian surface at Meridiani Planum using the Athena instrument payload [1], including the Alpha Particle X-Ray Spectrometer (APXS). The APXS has a small sensor head that is mounted on the robotic arm of the rover. The chemistry, mineralogy and morphology of selected samples were investigated by the APXS along with the Moessbauer Spectrometer (MB) and the Microscopic Imager (MI). The Rock Abrasion Tool (RAT) provided the possibility to dust and/or abrade rock surfaces down to several millimeters to expose fresh material for analysis. We report here on APXS data gathered along the nearly 6-kilometers long traverse in craters and plains of Meridiani.

Bruckner, J.↗

Mini-TES Observations of Comanche Carbonate and Its Distribution

The discovery by the Spirit rover of outcrops rich in Mg-Fe carbonate [Morris et al., 2010] represents another manifestation of a diverse aqueous history in Gusev crater. In 2005, observations by the Moessbauer spectrometer (MB) on outcrops dubbed Comanche provided initial indication of Fe-Mg carbonate that was subsequently supported by analysis of elemental data from the Alpha Particle X-ray Spectrometer (APXS). The recognition of a carbonate component in thermal infrared spectra measured by the Miniature Thermal Emission Spectrometer (Mini-TES) was significantly delayed due to dust contamination of the instrument's optics. With the implementation of a viable dust correction, the Comanche spectra were revisited and presented clear and compelling evidence for a Mg-Fe carbonate component that could be as much as a third of the total mineral abundance. The data from all three instruments in combination are best matched by Mg-Fe carbonate with an abundance of 16-34 wt%. Mini-TES spectra were acquired for 12 targets at various locations on the Comanche (4-5 m long) and Comanche Spur (1-2 m long) outcrops, the latter being the location of the MB and APXS measurements. The two outcrops are spectrally comparable and share similar morphology and texture based on color images from the Panoramic Camera (Pancam). The highest quality Mini-TES spectrum comes from the larger Comanche outcrop on a target named Saupitty. Linear least squares modeling of the Saupitty spectrum employed a library of laboratory spectra tailored for consistency with the APXS and MB data and included spectra representing Martian dust, a slope spectrum to account for any temperature determination errors, and a blackbody spectrum to account for differences in spectral contrast between the laboratory and Mini-TES spectrum. Successful modeling of the Comanche Saupitty spectrum required one or more carbonate phases to obtain a good fit. Excluding all carbonates from the full starting library more than doubled the root-mean-squared error of the model fit (0.147% vs. 0.299%). Because Mg-Fe carbonate and Ca-Mg carbonate (dolomite) are so spectrally similar over the range used for modeling, both provide a comparable fit. However, Carich carbonates like dolomite are precluded based on APXS data and are inconsistent with MB results. The Comanche carbonate rocks are stratigraphically above a set of olivine-rich volcaniclastic rocks known as Algonquin class that mantle the Haskin Ridge feature of the Columbia Hills. Based on ~50 Mini-TES observations, the Comanche outcrops are the only rocks that host abundant carbonate. However, a target at the base of the larger Comanche outcrop appears spectrally transitional between the carbonate and olivine units. This transitional spectral character applies to additional outcrops a few 10s of meters away from Comanche that also appear stratigraphically transitional. Additional work will attempt to establish whether we are seeing an alteration horizon or depositional unit associated with the emplacement Comanche carbonate.

Ruff, Steven W.↗

(abstract) The Alpha-Proton-X-ray Spectrometer Deployment Mechanism -- An Anthropomorphic Approach to Sensor Placement on Martian Rocks and Soil

The Mars Pathfinder mission promises to reap a harvest of geological information about Mars. One of the nearly half dozen instruments making this science data possible is the alpha proton X ray spectrometer (APXS). Using a curium source and backscattering techniques, the APXS will determine the elemental composition of rocks and the soil around the landing site. To ensure information of high fidelity, the APXS sensor face must be aligned to within 20° to the surface of each rock and soil sampling location and be held there for up to 10 hours. This is accomplished through the anthropomorphic deployment mechanism (ADM). The ADM mounts on the back of the Mars rover. Working with the rover, the ADM both actively and passively positions the APXS sensor head against a chosen target. The ADM is an amalgamation of unique solutions to some very challenging design problems. The resulting design is light, flexible, and nearly autonomous. Its straightforward operation rivals that of the human arm in simplicity and elegance.

Mars↗

Planetary surface exploration: MESUR/autonomous lunar rover

Planetary surface exploration micro-rovers for collecting data about the Moon and Mars was designed by the Department of Mechanical Engineering at the University of Idaho. The goal of both projects was to design a rover concept that best satisfied the project objectives for NASA-Ames. A second goal was to facilitate student learning about the process of design. The first micro-rover is a deployment mechanism for the Mars Environmental SURvey (MESUR) Alpha Particle/Proton/X-ray instruments (APX). The system is to be launched with the sixteen MESUR landers around the turn of the century. A Tubular Deployment System and a spiked-legged walker was developed to deploy the APX from the lander to the Martian surface. While on Mars the walker is designed to take the APX to rocks to obtain elemental composition data of the surface. The second micro-rover is an autonomous, roving vehicle to transport a sensor package over the surface of the moon. The vehicle must negotiate the lunar-terrain for a minimum of one year by surviving impacts and withstanding the environmental extremes. The rover is a reliable track-driven unit that operates regardless of orientation which NASA can use for future lunar exploratory missions. A detailed description of the designs, methods, and procedures which the University of Idaho design teams followed to arrive at the final designs are included.

Stauffer, Larry↗

Planetary surface exploration MESUR/autonomous lunar rover

Planetary surface exploration micro-rovers for collecting data about the Moon and Mars have been designed by the Department of Mechanical Engineering at the University of Idaho. The goal of both projects was to design a rover concept that best satisfied the project objectives for NASA/Ames. A second goal was to facilitate student learning about the process of design. The first micro-rover is a deployment mechanism for the Mars Environmental Survey (MESUR) Alpha Particle/Proton/X-ray (APX) Instrument. The system is to be launched with the 16 MESUR landers around the turn of the century. A Tubular Deployment System and a spiked-legged walker have been developed to deploy the APX from the lander to the Martian Surface. While on Mars, the walker is designed to take the APX to rocks to obtain elemental composition data of the surface. The second micro-rover is an autonomous, roving vehicle to transport a sensor package over the surface of the moon. The vehicle must negotiate the lunar terrain for a minimum of one year by surviving impacts and withstanding the environmental extremes. The rover is a reliable track-driven unit that operates regardless of orientation that NASA can use for future lunar exploratory missions. This report includes a detailed description of the designs and the methods and procedures which the University of Idaho design teams followed to arrive at the final designs.

Stauffer, Larry↗

The Athena Mars Rover Science Payload

The Mars Surveyor missions that will be launched in April of 2001 will include a highly capable rover that is a successor to the Mars Pathfinder mission's Sojourner rover. The design goals for this rover are a total traverse distance of at least 10 km and a total lifetime of at least one Earth year. The rover's job will be to explore a site in Mars' ancient terrain, searching for materials likely to preserve a record of ancient martian water, climate, and possibly biology. The rover will collect rock and soil samples, and will store them for return to Earth by a subsequent Mars Surveyor mission in 2005. The Athena Mars rover science payload is the suite of scientific instruments and sample collection tools that will be used to perform this job. The specific science objectives that NASA has identified for the '01 rover payload are to: (1) Provide color stereo imaging of martian surface environments, and remotely-sensed point discrimination of mineralogical composition. (2) Determine the elemental and mineralogical composition of martian surface materials. (3) Determine the fine-scale textural properties of these materials. (4) Collect and store samples. The Athena payload has been designed to meet these objectives. The focus of the design is on field operations: making sure the rover can locate, characterize, and collect scientifically important samples in a dusty, dirty, real-world environment. The topography, morphology, and mineralogy of the scene around the rover will be revealed by Pancam/Mini-TES, an integrated imager and IR spectrometer. Pancam views the surface around the rover in stereo and color. It uses two high-resolution cameras that are identical in most respects to the rover's navigation cameras. The detectors are low-power, low-mass active pixel sensors with on-chip 12-bit analog-to-digital conversion. Filters provide 8-12 color spectral bandpasses over the spectral region from 0.4 to 1.1 micron Narrow-angle optics provide an angular resolution of 0.28 mrad/pixel, nearly a factor of four higher than that of the Mars Pathfinder and Mars Surveyor '98 cameras. Image compression will be performed using a wavelet compression algorithm. The Mini-Thermal Emission Spectrometer (Mini-TES) is a point spectrometer operating in -the thermal IR. It produces high spectral resolution (5 /cm) image cubes with a wavelength range of 5-40 gm, a nominal signal/noise ratio of 500:1, and a maximum angular resolution of 7 mrad (7 cm at a distance of 10 in). The wavelength region over which it operates samples the diagnostic fundamental absorption features of rockforming minerals, and also provides some capability to see through dust coatings that could tend to obscure spectral features. The mineralogical information that Mini-TES provides will be used to select from a distance the rocks and soils that will be investigated in more detail and ultimately sampled. Mini-TES is derived from the MO/MGS TES instrument, but is significantly smaller and simpler. The instrument uses an 8-cm Cassegrain telescope, a Michelson interferometer, and uncooled pyroelectric detectors. Along with its mineralogical capabilities, Mini-TES can provide information on the thermophysical properties of rocks and soils. Viewing upward, it can also provide temperature profiles through the martian atmospheric boundary layer. Elemental and Mineralogical Composition: Once promising samples have been identified from a distance using Pancam/Mini-TES, they will be studied in detail using up to three compositional sensors that can be placed directly against them by an Instrument Arm. The two compositional sensors, presently on the payload are an Alpha-Proton-X-Ray Spectrometer (APXS), and a Mossbauer Spectrometer. The APXS is derived closely from the instrument that flew on Mars Pathfinder. Radioactive alpha sources and three detection modes (alpha, proton, and x-ray) provide elemental abundances of rocks and soils to complement and constrain mineralogical data. The Athena APXS will have a revised mechanical design that will cut down significantly on backscattering of alpha particles from martian atmospheric carbon. It will also include a target of known elemental composition that will be used for calibration purposes. The Athena Mossbauer Spectrometer is a diagnostic instrument for the mineralogy and oxidation state of Fe-bearing phases, which are particularly important on Mars. The instrument measures the resonant absorption of gamma rays produced by a Co-57 source to determine splitting of nuclear energy levels in Fe atoms that is related to the electronic environment surrounding them. It has been under development for space flight for many years at the Technical University of Darmstadt. The Mossbauer Spectrometer (and the other arm instruments) will be able to view a small permanent magnet array that will attract magnetic particles in the martian soil. The payload may also include a Raman Spectrometer. If included, the Raman Spectrometer will provide precise identification of major and minor mineral phases. It requires no sample preparation, and is also sensitive to organics. Fine-Scale Texture: The Instrument Arm a also carries a Microscopic Imager that will obtain high-resolution monochromatic images of the same materials for which compositional data will be obtained. Its spatial resolution is 20 micron/pixel over a 1 cm depth of field, and 40 micron/pixel over a 1-cm depth of field. Like Pancam, it uses the same active pixel sensor detectors and electronics as the rover's navigation cameras. The Instrument Arm is a three degree-of-freedom arm that uses designs and components from the Mars Pathfinder and Mars Surveyor '98 projects. Its primary function is instrument positioning. Along with the instruments noted above, it also carries a brush that can be used to remove dust and other loose coatings from rocks. Sample Collection and Storage: Martian rock and soil samples will be collected using a low-power rotary coring drill called the Mini-Corer. An important characteristic of this device is that it can obtain intact samples of rock from up to 5 cm within strong boulders and bedrock, Nominal core dimensions are 8xl7 mm. The Mini-Corer drills a core to the commanded depth in a rock, shears it off, retains it, and extracts it. It can also acquire samples of loose soil, using soil sample cups that are pressed downward into loose material. The Mini-Corer can drill at angles from vertical to 45' off vertical. It has six interchangeable bits for long life. Mechanical damage to the sample during drilling is minimal, and heating is negligible. After acquisition, the sample may be viewed by the arm instruments, and/or placed in one of 104 compartments in the Sample Container. A subset of the acquired samples may be replaced with other samples obtained later if desired. The Sample Container has no moving parts, and is mounted external to the rover for easy removal by the Mars Surveyor 2005 flight system. Operation of the rover will make extensive use of automated onboard navigation and hazard avoidance capabilities. Otherwise, use of onboard autonomy is minimal. Data downlink capability is about 40 Mbit/sol, and the use of the Mars Surveyor '01 orbiter for data relay imposes a limit of at most two command cycles per sol. Because of the significant amount of time available between command cycles, all payload elements will be operated sequentially, rather than in parallel.; this approach also significantly simplifies operations and minimizes peak power usage. The landing site for the '01 rover has not been selected yet. Site selection will make as full use as possible of Mars Global Surveyor data, and will involve substantial input from the broad Mars science community. Summary: The following table describes the mass, power, providers, and key scientific objectives of all the major elements of the Athena payload. Additional Athena payload information may be found at: http://astrosun.tn.cornell.edu/athena/index.html. Additional information contained in the original.

Squyes, S. W.↗

Results of the Alpha-Particle-X-Ray Spectrometer on Board of the Mars Exploration Rovers

The Mars Exploration Rovers Spirit and Opportunity landed at Gusev crater and Meridiani Planum. The Alpha Particle X-ray Spectrometer (APXS) is part of the instrument suite on both rovers. It is equipped with six 244Cm sources which provide x-ray excitation with alpha-particles (PIXE) and x-ray radiation (XRF). This combination allows x-ray spectroscopy of elements from Na to Br in the energy range of 0.9 to 16 keV. X-ray detectors with a high energy resolution of 160 eV at Fe K allow us to separate even closely spaced energy peaks, such as Na, Mg, Al and Si. The APXS is attached to the rover s arm and provides in-situ measurements of the chemical composition of soils, surfaces of rocks and outcrops and their abraded surfaces. This abstract gives an overview of APXS results obtained during the first year of operation on both landing sites.

Geller, R.↗

Chemical Diversity along the Traverse of the Rover Spirit at Gusev Crater

The Alpha-Particle-X-ray Spectrometer (APXS) is part of the in situ payload of the Mars Exploration Rovers. It has determined the chemical composition of soils and rocks along the nearly 6 km long traverse of the rover Spirit. The measuring method a combination of PIXE and XRF using Cm244 sources - allowed the unambiguous identification of elemental compositions with high precision. Besides sample triage and quantification of saltforming elements as indicators for aqueous alteration, the APXS also delivered important constraints to mineralogy intruments (i.e., Mossbauer (MB), MiniTES, Pancam) on minerals and rock types. The mineralogy instruments on the other hand provided constraints on minerals used for APXS normative calculations and, e.g. allowed the attribution of S to sulfate, instead of sulfide or elemental sulfur. This abstract gives an updated overview of the data obtained up to our current rover position on sol 720 at the eastern base of the Columbia Hills. We will emphasize elemental correlations that imply the presence of certain minerals that can not be identified by the MER mineralogy instruments.

Gellert, R.↗

Hematite-Rich Fracture Fill at Meridiani Planum, Mars: Implications for Fluid Chemistry

The Mars Exploration Rover Opportunity has been operating at the surface of Mars for over 2100 sols and has driven a distance of approximately 20 km. Throughout the traverse, outcrop rocks with margins and fracture fill resistant to erosion have been imaged and analyzed in detail by the Moessbauer (MB) spectrometer and the Alpha Particle X-ray Spectrometer (APXS). A recent APXS analysis of an outcrop block excavated by a young impact crater shows a coating with the highest concentration of iron measured by either rover, not including the iron-nickel meteorites. Texturally, this sample (referred to as "Chocolate Hills -Aloya") appears as a cemented collection of partially fragmented \blueberries." With the exception of an elevated sulfur content, the elemental chemistry of this particular sample is entirely consistent with other analyses of hematite spherules at Merdiani Planum. As a result, it is difficult to determine whether this coating, which may have been filling a fracture in outcrop rocks prior to disruption by the impact, was simply an agglomeration of spherules or a result of a more complicated aqueous process. In contrast, a number of other fracture-filling exposures and erosion-resistant rinds have been analyzed by the APXS and MB instruments showing significant concentrations of iron in the form of hematite without the texture of spherule fragments. In one of these samples, a broken piece of fracture fill within Victoria crater referred to as "Dorsal," showed over 50% of the iron in hematite, the highest Mn concentration of any sample measured by the rovers, and elevated levels of Cl and Br. While the Fe:Mn ratio of the Dorsal analyses are comparable to that of Gusev and Meridiani basalts, it is clear that chemistry of this sample cannot be completely explained by a simple mixing of outcrop and blueberry compositions

Yen, Albert↗

The XRD Amorphous Component in John Klein Drill Fines at Yellowknife Bay, Gale Crater, Mars

Drill fines of mudstone (targets John Klein and Cumberland) from the Sheepbed unit at Yel-lowknife Bay were analyzed by MSL payload elements including the Chemistry and Mineralogy (CheMin), APXS (Alpha Particle X-Ray Spectrometer), and Sample Analysis at Mars (SAM) instruments. CheMin XRD results show a variety of crystalline phases including feldspar, pyroxene, olivine, oxides, oxyhydroxides, sulfates, sulfides, a tri-octahedral smectite, and XRD amorphous material. The drill fines are distinctly different from corresponding analyses of the global soil (target Rocknest) in that the mudstone samples contained detectable phyllosilicate. Here we focus on John Klein and combine CheMin and APXS data to calculate the chemical composition and concentration of the amorphous component. The chemical composition of the amorphous plus smectite component for John Klein was calculated by subtracting the abundance-weighted chemical composition of the individual XRD crystalline components from the bulk composition of John Kline as measured by APXS. The chemical composition of individual crystalline components was determined either by stoichiometry (e.g., hematite and magnetite) or from their unit cell parameters (e.g., feldspar, olivine, and pyroxene). The chemical composition of the amorphous + smectite component (approx 71 wt.% of bulk sample) and bulk chemical composition are similar. In order to calculate the chemical composition of the amorphous component, a chemical composition for the tri-octahedral smectite must be assumed. We selected two tri-octahedral smectites with very different MgO/(FeO + Fe2O3) ratios (34 and 1.3 for SapCa1 and Griffithite, respectively). Relative to bulk sample, the concentration of amorphous and smectite components are 40 and 29 wt.% for SapCa1 and 33 and 36 wt.% for Griffithite. The amount of smectite was calculated by requiring the MgO concentration to be approx 0 wt.% in the amorphous component. Griffithite is the preferred smectite because the position of its 021 diffraction peak is similar to that reported for John Klein. In both cases, the amorphous component has low SiO2 and MgO and high FeO + Fe2O3, P2O5, and SO3 concentrations relative to bulk sample. The chemical composition of the bulk drill fines and XRD crystalline, smectite, and amorphous components implies alteration of an initially basaltic material under near neutral conditions (not acid sulfate), with the sulfate incorporated later as veins of CaSO4 injected into the mudstone.

Morris, Richard V.↗

Recognizing Sulfate and Phosphate Complexes Adsorbed onto Nanophase Weathering Products on Mars

Nanophase weathering products (i.e., secondary phases that lack long-range atomic order) have been recognized on the martian surface via orbital observations and in-situ measurements from landed missions. Allophane, a poorly crystalline, hydrated aluminosilicate, has been identified at the regional scale in models of thermal-infrared (TIR) data from the Thermal Emission Spectrometer (TES) and at the local scale from visible/near-IR (VNIR) data from the Compact Reconnaissance Impact Spectrometer for Mars (CRISM) instrument and phase calculations of Alpha Particle X-ray Spectrometer (APXS) data of rocks encountered by the Mars Exploration Rovers (MER) Spirit and Opportunity. Nanophase iron oxides (npOx) have been recognized in rocks and soils measured by the Mössbauer Spectrometer on Spirit and Opportunity. Furthermore, analyses of X-ray diffraction data measured by the CheMin instrument onboard the Mars Science Laboratory rover Curiosity indicate rock and soil samples are comprised of approx. 20-50 wt.% X-ray amorphous materials. Chemical measurements by landed missions indicate the presence of sulfur and phosphorus in martian rocks in soils, and APXS data from Gusev crater demonstrate abundances of up to approx. 5 wt.% P2O5 and approx. 30 wt.% SO3. However, the speciation of phosphorus and sulfur is not always evident. On Earth, phosphate and sulfate anions can be chemisorbed onto the surfaces of nanophase weathering products. This process may also occur on Mars, and calculations of the composition of the amorphous component at Gale crater using CheMin mineral models and APXS data show that amorphous material is enriched in volatiles, including S. Here, we examine the ability to detect chemisorbed sulfate and phosphate complexes by analyzing sulfate- and phosphate-adsorbed nanophase weathering products using instruments similar to those on landed and orbital missions.

Rampe, E. B.↗

Oxychlorine Species on Mars: The Gale Crater Story

Comparing data from the Alpha- Particle X-Ray Spectrometer (APXS) and the Sample Analysis at Mars (SAM) instruments on MSL reveals a strong linear correlation between chlorine and oxygen, further demonstrating the presence of oxychlorine species in Gale Crater and, very likely, globally on Mars. Perchlorate was first discovered on Mars by the Microscopy, Electrochemistry, and Conductivity Analyzer (MECA) instrument on the Phoenix lander in 2008. Current hypotheses suggest that the formation of oxychlorine species such as perchlorate or chlorate is a global process and that these species should be globally distributed on Mars [e.g. 2-4]. To date, the SAM and Chemistry and Mineralogy (CheMin) instruments on MSL have analyzed one scooped sample of aeolian material (Rocknest [RN]), and four drilled samples (John Klein [JK], Cumberland [CB], Windjana [WJ], and Confidence Hills [CH]). The APXS instrument has also investigated the same or very similar samples. Although not definitively identified, oxychlorine species have been proposed to explain releases of O2, HCl, and chlorinated hydrocarbon species detected by evolved gas analysis (EGA) with the SAM instrument. We report a strong linear correlation between wt. % Cl detected by APXS and moles O2 detected by SAM during pyrolysis, indicating the presence of oxychlorine species in Gale Crater.

Archer, P. D., Jr.↗