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Achilles, C. N.

Publications and source records attributed to Achilles, C. N..

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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.↗

Evidence for Acid-Sulfate Alteration in the Pahrump Hills Region, Gale Crater, Mars

The Pahrump Hills region of Gale crater is a approximately 12 millimeter thick section of sedimentary rock in the Murray formation, interpreted as the basal geological unit of Mount Sharp. The Mars Science Laboratory, Curiosity, arrived at the Pahrump Hills in September 2014 and performed a detailed six-month investigation of the sedimentary structures, geochemistry, and mineralogy of the area. During the campaign, Curiosity drilled and delivered three mudstone samples (targets Confidence Hills, Mojave 2, and Telegraph Peak) to its internal instruments, including the CheMin XRD/XRF.

Rampe, E. B.↗

Mineralogy of the Pahrump Hills Region, Gale Crater, Mars

The Pahrump Hills region of Gale crater is a approximately 12 millimeter thick section of sedimentary rocks in the Murray formation, interpreted as the basal geological unit of Mount Sharp. The Mars Science Laboratory, Curiosity, arrived at the Pahrump Hills in September, 2014, and performed a detailed six-month investigation of the sedimentary structures, geochemistry, and mineralogy of the area. During the campaign, Curiosity drilled and delivered three rock samples to its internal instruments, including the CheMin XRD/XRF. The three targets, Confidence Hills, Mojave 2, and Telegraph Peak, contain variable amounts of plagioclase, pyroxene, iron oxides, jarosite, phyllosilicates, and X-ray amorphous material. Hematite was predicted at the base of Mount Sharp from orbital visible/near-IR spectroscopy, and CheMin confirmed this detection. The presence of jarosite throughout Pahrump Hills suggests the sediments experienced acid-sulfate alteration, either in-situ or within the source region of the sediments. This acidic leaching environment is in stark contrast to the environment preserved within the Sheepbed mudstone on the plains of Gale crater. The minerals within Sheepbed, including Fe-saponite, indicate these sediments were deposited in a shallow lake with circumneutral pH that may have been habitable.

Rampe, E. B.↗

Amorphous Analogs of Martian Global Soil: Pair Distribution Function Analyses and Implications for Scattering Models of Chemin X-ray Diffraction Data

Soils on Mars have been analyzed by the Mars Exploration Rovers (MER) and most recently by the Mars Science Laboratory (MSL) rover. Chemical analyses from a majority of soil samples suggest that there is a relatively uniform global soil composition across much of the planet. A soil site, Rocknest, was sampled by the MSL science payload including the CheMin X-ray diffractometer and the Alpha Particle X-ray Spectrometer (APXS). Che- Min X-ray diffraction (XRD) data revealed crystalline phases and a broad, elevated background, indicating the presence of amorphous or poorly ordered materials (Fig 1). Based on the chemical composition of the bulk soil measured by APXS and the composition of crystalline phases derived from unit-cell parameters determined with CheMin data, the percentages of crystalline and amorphous phases were calculated at 51% and 49%, respectively. Attempts to model the amorphous contribution to CheMin XRD patterns were made using amorphous standards and full-pattern fitting methods and show that the broad, elevated background region can be fitted by basaltic glass, allophane, and palagonite. However, the modeling shows only that these phases have scattering patterns similar to that for the soil, not that they represent unique solutions. Here, we use pair distribution function (PDF) analysis to determine the short-range order of amorphous analogs in martian soils and better constrain the amorphous material detected by CheMin.

Achilles, C. N.↗

Update on the Chemical Composition Of Crystalline, Smectite, and Amorphous Components for Rocknest Soil and John Klein and Cumberland Mudstone Drill Fines at Gale Crater, Mars

We have previously calculated the chemical compositions of the X-ray-diffraction (XRD) amorphous component of three solid samples (Rocknest (RN) soil, John Klein (JK) drill fines, and Cumberland (CB) drill fines) using major-element chemistry (APXS), volatile-element chemistry (SAM), and crystalline- phase mineralogy (CheMin) obtained by the Curiosity rover as a part of the ongoing Mars Science Laboratory mission in Gale Crater. According to CheMin analysis, the RN and the JK and CB samples are mineralogically distinct in that RN has no detectable clay minerals and both JK and CB have significant concentrations of high-Fe saponite. The chemical composition of the XRD amorphous component is the composition remaining after mathematical removal of the compositions of crystalline components, including phyllosilicates if present. Subsequent to, we have improved the unit cell parameters for Fe-forsterite, augite, and pigeonite, resulting in revised chemical compositions for the XRD-derived crystalline component (excluding clay minerals). We update here the calculated compositions of amorphous components using these revised mineral compositions.

Morris, R. V.↗

Potential Cement Phases in Sedimentary Rocks Drilled by Curiosity at Gale Crater, Mars

The Mars Science Laboratory rover Curiosity has encountered a variety of sedimentary rocks in Gale crater with different grain sizes, diagenetic features, sedimentary structures, and varying degrees of resistance to erosion. Curiosity has drilled three rocks to date and has analyzed the mineralogy, chemical composition, and textures of the samples with the science payload. The drilled rocks are the Sheepbed mudstone at Yellowknife Bay on the plains of Gale crater (John Klein and Cumberland targets), the Dillinger sandstone at the Kimberley on the plains of Gale crater (Windjana target), and a sedimentary unit in the Pahrump Hills in the lowermost rocks at the base of Mt. Sharp (Confidence Hills target). CheMin is the Xray diffractometer on Curiosity, and its data are used to identify and determine the abundance of mineral phases. Secondary phases can tell us about aqueous alteration processes and, thus, can help to elucidate past aqueous environments. Here, we present the secondary mineralogy of the rocks drilled to date as seen by CheMin and discuss past aqueous environments in Gale crater, the potential cementing agents in each rock, and how amorphous materials may play a role in cementing the sediments.

Rampe, E. B.↗

Confidence Hills Mineralogy and Chemin Results from Base of Mt. Sharp, Pahrump Hills, Gale Crater, Mars

The Mars Science Laboratory (MSL) rover Curiosity recently completed its fourth drill sampling of sediments on Mars. The Confidence Hills (CH) sample was drilled from a rock located in the Pahrump Hills region at the base of Mt. Sharp in Gale Crater. The CheMin X-ray diffractometer completed five nights of analysis on the sample, more than previously executed for a drill sample, and the data have been analyzed using Rietveld refinement and full-pattern fitting to determine quantitative mineralogy. Confidence Hills mineralogy has several important characteristics: 1) abundant hematite and lesser magnetite; 2) a 10 angstrom phyllosilicate; 3) multiple feldspars including plagioclase and alkali feldspar; 4) mafic silicates including forsterite, orthopyroxene, and two types of clinopyroxene (Ca-rich and Ca-poor), consistent with a basaltic source; and 5) minor contributions from sulfur-bearing species including jarosite.

Cavanagh, P. D.↗

Griffith Saponite as an Analog for Clay Minerals at Yellowknife Bay in Gale Crater, Mars: A Marker for Low-temperature Hydrothermal Processes

The CheMin X-ray diffraction (XRD) instrument onboard the Mars Science Laboratory rover Curiosity in Gale Crater, Mars, discovered smectite in drill fines of the Sheepbed mudstone at Yellowknife Bay (YNB). The mudstone has a basaltic composition, and the XRD powder diffraction pattern shows smectite 02l diffraction bands peaking at 4.59 A for targets John Klein and Cumberland, consistent with tri-octahedral smectites (saponite). From thermal analysis, the saponite abundance is ~20 wt. %. Among terrestrial analogues we have studied, ferrian saponite from Griffith Park (Los Angeles, CA) gives the best match to the position of the 02l diffraction band of YNB saponites. Here we describe iron-rich saponites from a terrestrial perspective, with a focus on Griffith saponite, and discuss their implications for the mineralogy of Sheepbed saponite and its formation pathways. Iron-rich saponite: Iron-rich saponite on the Earth is recognized as a low-temperature (<100 C), authigenic alteration product of basalt [e.g., 4-16]. In the discussion that follows, we reference the position of the 02l band because it is a measure of the unit cell 'b' dimension of the octahedral layer and thus the cations (including Fe redox state) in the octahedral layer. Ordinarily, the 06l band near 1.5 A is used to determine the 'b' dimension of smectite, but this band is not accessible with MSL CheMin instrument. For reference, a ferrosaponite (i.e., Fe2+ saponite) studied by [15] has a 02l spacing of 4.72 A and Fe3+/Fe = 0.27 [15]. Samples of terrestrial ferrosaponite, however, are reported to oxidize on the timescale of days when removed from their natural environment and not protected from oxidation. The Griffith saponite is Mg-rich ferrian saponite, and sample AMNH 89172 has an 02l spacing of 4.59 A (same as the Sheepbed saponites) and Fe3+/Fe = 0.64 [3]. This similarity suggests that Sheepbed saponites are ferrian (incompletely oxidized ferrosaponite). More oxidized Griffith saponites (Fe3+/Fe > 0.90) have somewhat smaller 02l d-spacings and also show Mossbauer evidence for an XRD amorphous Fe-bearing phase (e.g., ferrihydrite, hisingerite, superparamagnetic ferric oxides, etc.). The Griffith saponite occurs as vesicle fills, as replacements of olivine, and as replacements of mesostasis (basaltic glass). Similar occurrence modes are reported elsewhere. Hisingerite has been proposed by [13] as the alteration product of ferrian saponite whose precursor by oxidation was ferrosaponite.

Morris, R.V.↗

Amorphous Phases on the Surface of Mars

Both primary (volcanic/impact glasses) and secondary (opal/silica, allophane, hisingerite, npOx, S-bearing) amorphous phases appear to be major components of martian surface materials based on orbital and in-situ measurements. A key observation is that whereas regional/global scale amorphous components include altered glass and npOx, local scale amorphous phases include hydrated silica/opal. This suggests widespread alteration at low water-to-rock ratios, perhaps due to snow/ice melt with variable pH, and localized alteration at high water-to-rock ratios. Orbital and in-situ measurements of the regional/global amorphous component on Mars suggests that it is made up of at least three phases: npOx, amorphous silicate (likely altered glass), and an amorphous S-bearing phase. Fundamental questions regarding the composition and the formation of the regional/global amorphous component(s) still remain: Do the phases form locally or have they been homogenized through aeolian activity and derived from the global dust? Is the parent glass volcanic, impact, or both? Are the phases separate or intimately mixed (e.g., as in palagonite)? When did the amorphous phases form? To address the question of source (local and/or global), we need to look for variations in the different phases within the amorphous component through continued modeling of the chemical composition of the amorphous phases in samples from Gale using CheMin and APXS data. If we find variations (e.g., a lack of or enrichment in amorphous silicate in some samples), this may imply a local source for some phases. Furthermore, the chemical composition of the weathering products may give insight into the formation mechanisms of the parent glass (e.g., impact glasses contain higher Al and lower Si [30], so we might expect allophane as a weathering product of impact glass). To address the question of whether these phases are separate or intimately mixed, we need to do laboratory studies of naturally altered samples made up of mixed phases (e.g., palagonite) and synthetic single phases to determine their short-range order structures and calculate their XRD patterns to use in models of CheMin data. Finally, to address the timing of the alteration, we need to study rocks on the martian surface of different ages that may contain glass (volcanic or impact) with MSL and future rovers to better understand how glass alters on the martian surface, if that alteration mechanism is universal, and if alteration spans across long periods of time or if there is a time past which unaltered glass remains.

Rampe, E. B.↗

Basaltic Soil of Gale Crater: Crystalline Component Compared to Martian Basalts and Meteorites

A significant portion of the soil of the Rocknest dune is crystalline and is consistent with derivation from unweathered basalt. Minerals and their compositions are identified by X-ray diffraction (XRD) data from the CheMin instrument on MSL Curiosity. Basalt minerals in the soil include plagioclase, olivine, low- and high-calcium pyroxenes, magnetite, ilmenite, and quartz. The only minerals unlikely to have formed in an unaltered basalt are hematite and anhydrite. The mineral proportions and compositions of the Rocknest soil are nearly identical to those of the Adirondack-class basalts of Gusev Crater, Mars, inferred from their bulk composition as analyzed by the MER Spirit rover.

Treiman, A. H.↗

Crystal-Chemical Analysis of Soil at Rocknest, Gale Crater

The CheMin instrument on the Mars Science Laboratory rover Curiosity performed X-ray diffraction analysis on Martian soil [1] at Rocknest in Gale Crater. In particular, crystalline phases from scoop 5 were identified and analyzed with the Rietveld method [2]. Refined unit-cell parameters are reported in Table 1. Comparing these unit-cell parameters with those in the literature provides an estimate of the chemical composition of the crystalline phases. For instance, Fig. 1 shows the Mg-content of Fa-Fo olivine as a function of the b unit-cell parameter using literature data. Our refined b parameter is indicated by the black triangle.

Morrison, S. M.↗

First X-Ray Diffraction Results from Mars Science Laboratory: Mineralogy of Rocknest Aeolian Bedform at Gale Crater

Numerous orbital and landed observations of the martian surface suggest a reasonably uniform martian soil composition, likely as a result of global aeolian mixing [1, 2]. Chemical data for martian soils are abundant [e.g., 2, 3], and phase information has been provided by lander thermal emission and Moessbauer spectroscopic measurements [3, 4, 5, 6]. However, until now no X-ray diffraction (XRD) data were available for martian soil nor has XRD ever been used on another body apart from Earth. XRD is generally considered the most definitive method for determining the crystalline phases in solid samples, and it is the method of choice for determining mineralogy. CheMin s first XRD analysis on Mars coincided with the 100th anniversary of the discovery of X-ray diffraction by von Laue. Curiosity delivered scooped samples of loose, unconsolidated material ("soil") acquired from an aeolian bedform at the Rocknest locality to instruments in the body of the rover (the laboratory). Imaging shows that the soil has a range of particle sizes, of 1-2 mm and smaller, presumably representing contributions from global, regional, and local sources.

Bish, D. L.↗

CheMin Instrument Performance and Calibration on Mars

The CheMin (Chemistry and Mineralogy) instrument on the Mars Science Laboratory rover Curiosity uses a CCD detector and a Co-anode X-ray tube source to acquire both mineralogy (from the pattern of Co diffraction) and chemical information (from energies of fluoresced X-rays). A key component of the CheMin instrument is the ability to move grains within sample cells during analysis, providing multiple, random grain orientations that disperse diffracted X-ray photons along Debye rings rather than producing discrete Laue spots. This movement is accomplished by piezoelectric vibration of the sample cells. A cryocooler is used to maintain the CCD at a temperature at about -50 C in order to obtain energy resolution better than 250 eV, allowing discrimination of diffracted Co K X-rays from Fe K and other fluorescent X-rays. A detailed description of CheMin is provided in [1]. The CheMin flight model (FM) is mounted within the body of Curiosity and has been operating on Mars since August 6, 2012. An essentially identical sister instrument, the CheMin demonstration model (DM), is operated in a Mars environment chamber at JPL.

Vaniman, D. T.↗

Detecting Nanophase Weathering Products with CheMin: Reference Intensity Ratios of Allophane, Aluminosilicate Gel, and Ferrihydrite

X-ray diffraction (XRD) data collected of the Rocknest samples by the CheMin instrument on Mars Science Laboratory suggest the presence of poorly crystalline or amorphous materials [1], such as nanophase weathering products or volcanic and impact glasses. The identification of the type(s) of X-ray amorphous material at Rocknest is important because it can elucidate past aqueous weathering processes. The presence of volcanic and impact glasses would indicate that little chemical weathering has occurred because glass is highly susceptible to aqueous alteration. The presence of nanophase weathering products, such as allophane, nanophase iron-oxides, and/or palagonite, would indicate incipient chemical weathering. Furthermore, the types of weathering products present could help constrain pH conditions and identify which primary phases altered to form the weathering products. Quantitative analysis of phases from CheMin data is achieved through Reference Intensity Ratios (RIRs) and Rietveld refinement. The RIR of a mineral (or mineraloid) that relates the scattering power of that mineral (typically the most intense diffraction line) to the scattering power of a separate mineral standard such as corundum [2]. RIRs can be calculated from XRD patterns measured in the laboratory by mixing a mineral with a standard in known abundances and comparing diffraction line intensities of the mineral to the standard. X-ray amorphous phases (e.g., nanophase weathering products) have broad scattering signatures rather than sharp diffraction lines. Thus, RIRs of X-ray amorphous materials are calculated by comparing the area under one of these broad scattering signals with the area under a diffraction line in the standard. Here, we measured XRD patterns of nanophase weathering products (allophane, aluminosilicate gel, and ferrihydrite) mixed with a mineral standard (beryl) in the CheMinIV laboratory instrument and calculated their RIRs to help constrain the abundances of these phases in the Rocknest samples.

Rampe, E. B.↗

Mineralogy and Elemental Composition of Wind Drift Soil at Rocknest, Gale Crater

The Mars Science Laboratory rover Curiosity has been exploring Mars since August 5, 2012, conducting engineering and first-time activities with its mobility system, arm, sample acquisition and processing system (SA/SPaH-CHIMRA) and science instruments. Curiosity spent 54 sols at a location named "Rocknest," collecting and processing five scoops of loose, unconsolidated materials ("soil") acquired from an aeolian bedform (Fig. 1). The Chemistry and Mineralogy (CheMin) instrument analyzed portions of scoops 3, 4, and 5, to obtain the first quantitative mineralogical analysis of Mars soil, and to provide context for Sample Analysis at Mars (SAM) measurements of volatiles, isotopes and possible organic materials.

Blake, D. F.↗

The Amorphous Component in Martian Basaltic Soil in Global Perspective from MSL and MER Missions

The mineralogy instrument CheMin onboard the MSL rover Curiosity analyzed by transmission XRD [1] the <150 microns size fraction of putative global basaltic martian soil from scoops 4 and 5 of the Rocknest aeolian bedform (sol 81-120). Here, we combine chemical (APXS) and mineralogical (Mossbauer; MB) results from the MER rovers with chemical (APXS) and mineralogical (CheMin) results from Curiosity to constrain the relative proportions of amorphous and crystalline components, the bulk chemical composition of those components, and the

Morris, R. V.↗

X-Ray Diffraction Reference Intensity Ratios of Amorphous and Poorly Crystalline Phases: Implications for CheMin on the Mars Science Laboratory

The CheMin instrument on the Mars Science Laboratory (MSL) rover Curiosity is an X-ray diffraction (XRD) and X-ray fluorescence (XRF) instrument capable of providing the mineralogical and chemical compositions of rocks and soils on the surface of Mars. CheMin uses a microfocus X-ray tube with a Co target, transmission geometry, and an energy-discriminating X-ray sensitive CCD to produce simultaneous 2-D XRD patterns and energy-dispersive X-ray histograms from powdered samples. Piezoelectric vibration of the cell is used to randomize the sample to reduce preferred orientation effects. Instrument details are provided in [1, 2, 3]. Analyses of rock and soil samples by the Mars Exploration Rovers (MER) show nanophase ferric oxide (npOx) is a significant component of the Martian global soil [4] and is thought to be one of the major contributing phases that the Curiosity rover will encounter if a soil sample is analyzed in Gale Crater. Because of the nature of this material, npOx will likely contribute to an X-ray amorphous or short-order component of a XRD pattern measured by the CheMin instrument.

Morris, R. V.↗