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NASA NTRS2014

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.↗
NASA NTRS2014

Comet C2012 S1 (ISON)s Carbon-rich and Micron-size-dominated Coma Dust

Comet C/2012 S1 (ISON) was unique in that it was a dynamically new comet derived from the Nearly Isotropic Oort cloud reservoir of comets with a sun-grazing orbit. We present thermal models for comet ISON (rh approx.1.15 AU, 2013-Oct-25 11:30 UT) that reveal comet ISON's dust was carbon-rich and dominated by a narrow size distribution dominated by approx. micron-sized grains. We constrained the models by our SOFIA FORCAST photometry at 11.1, 19.7 and 31.5 microns and by a silicate feature strength of approx.1.1 and an 8-13microns continuum greybody color temperature of approx. 275-280 K (using Tbb ∝ r−0.5 h and Tbb approx. 260-265 K from Subaru COMICS, 2013-Oct-19 UT)[1,2]. N-band spectra of comet ISON with the BASS instrument on the NASA IRTF (2013-Nov-11-12 UT) show a silicate feature strength of approx. 1.1 and an 11.2microns forsterite peak.[3] Our thermal models yield constraints the dust composition as well as grain size distribution parameters: slope, peak grain size, porosity. Specifically, ISON's dust has a low silicate-to- amorphous carbon ratio (approx. 1:9), and the coma size distribution has a steep slope (N4.5) such that the coma is dominated by micron-sized, moderately porous, carbon-rich dust grains. The N-band continuum color temperature implies submicronto micron-size grains and the steep fall off of the SOFIA far-IR photometry requires the size distribution to have fewer relative numbers of larger and cooler grains compared to smaller and hotter grains. A proxy for the dust production rate is fρ approx.1500 cm, akin to Afρ. ISON has a moderate-to-low dust-to-gas ratio. Comet ISON's dust grain size distribution does not appear similar to the few well-studied long-period Nearly Isotropic Comets (NICs), namely C/1995 O1 (Hale-Bopp) and C/2001 Q4 (NEAT) that had smaller and/or more highly porous grains and larger sizes, or C/2007 N4 (Lulin) and C/2006 P1 (McNaught) that had large and/or compact grains. Radial transport to comet-forming disk distances (≥ 20 AU) is easier for smaller grains (≤1 micron) than for larger grains (approx. 20 microns like Stardust terminal particles). The presence of predominantly micron-sized and smaller grains suggests comet ISON may have formed either earlier in disk evolution whereby larger grains did not have the time to be transported to distances beyond Neptune, or the comet formed so far out in the disk that larger grains did not traverse such large radial distances. The high carbon-content of ISON's refractory dust appears to be complimented by the presence of limitedlifetime organic (CHON-like) grain materials: preliminary analyses of near-IR and high-resolution optical spectra indicate that gas-phase daughter molecules C2, CN, and CH were more abundant than their parent molecules (C2H2, C2H6, measured in the near- IR). Dust composition as well as grain size distribution parameters (slope, peak grain size, and porosity) give clues to comet origins.

NASA/DLR Stratospheric Observatory↗
NASA NTRS2012

An Icy Kuiper Belt Around the Young Solar-type Star HD 181327

Context. HD 181327 is a young main sequence F5/F6 V star belonging to the Beta Pictoris moving group (age approx.. 12 Myr). It harbors an optically thin belt of circumstellar material at radius approx.. 90 AU, presumed to result from collisions in a population of unseen planetesimals. Aims. We aim to study the dust properties in the belt in details, and to constrain the gas-to-dust ratio. Methods. We obtained far-infrared photometric observations of HD 181327 with the PACS instrument onboard the Herschel Space Observatory, complemented by new 3.2 mm observations carried with the ATCA array. The geometry of the belt is constrained with newly reduced HST/NICMOS scattered light images that allow the degeneracy between the disk geometry and the dust properties to be broken. We then use the radiative transfer code GRaTeR to compute a large grid of models, and we identify the grain models that best reproduce the spectral energy distribution (SED) through a Bayesian analysis. We attempt to detect the oxygen and ionized carbon fine-structure lines with Herschel/PACS spectroscopy, providing observables to our photochemical code ProDiMo. Results. The HST observations confirm that the dust is confined in a narrow belt. The continuum is detected with Herschel/PACS completing nicely the SED in the far-infrared. The disk is marginally resolved with both PACS and ATCA. A medium integration of the gas spectral lines only provides upper limits on the [OI] and [CII] line fluxes.We show that the HD 181327 dust disk consists of micron-sized grains of porous amorphous silicates and carbonaceous material surrounded by an important layer of ice, for a total dust mass of approx.. 0.05 Solar Mass (in grains up to 1 mm). We discuss evidences that the grains consists of fluffy aggregates. The upper limits on the gas atomic lines do not provide unambiguous constraints: only if the PAH abundance is high, the gas mass must be lower than approx. 17 Solar Mass. Conclusions. Despite the weak constraints on the gas disk, the age of HD 181327 and the properties of the dust disk suggest that it has passed the stage of gaseous planets formation. The dust reveals a population of icy planetesimals, similar to the primitive Edgeworth-Kuiper belt, that may be a source for the future delivery of water and volatiles onto forming terrestrial planets.

HD 181327↗
NASA NTRS2014

A Novel Instrument and Methodology for the In-Situ Measurement of the Stress in Thin Films

We introduce a novel methodology for the in-situ measurement of mechanical stress during thin film growth utilizing a highly sensitive non-contact variation of the classic spherometer. By exploiting the known spherical deformation of the substrate the value of the stress induced curvature is inferred by measurement of only one point on the substrate's surface-the sagittal. From the known curvature the stress can be calculated using the well-known Stoney equation. Based on this methodology, a stress sensor has been designed which is simple, highly sensitive, compact, and low cost. As a result of its compact nature, the sensor can be mounted in any orientation to accommodate a given deposition geometry without the need for extensive modification to an already existing deposition system. The technique employs the use of a double side polished substrate that offers good specular reflectivity and is isotropic in its mechanical properties, such as <111> oriented crystalline silicon or amorphous soda lime glass, for example. The measurement of the displacement of the uncoated side during deposition is performed with a high resolution (i.e. 5nm), commercially available, inexpensive, fiber optic sensor which can be used in both high vacuum and high temperature environments (i.e. 10(exp-7) Torr and 480oC, respectively). A key attribute of this instrument lies in its potential to achieve sensitivity that rivals other measurement techniques such as the micro cantilever method but, due to the comparatively larger substrate area, offers a more robust and practical alternative for subsequent measurement of additional characteristics of the film that can might be correlated to film stress. We present measurement results of nickel films deposited by magnetron sputtering which show good qualitative agreement to the know behavior of polycrystalline films previously reported by Hoffman.

Broadway, David M.↗
NASA NTRS2014

Chemical Sharpening, Shortening, and Unzipping of Boron Nitride Nanotubes

Boron nitride nanotubes (BNNTs), the one-dimensional member of the boron nitride nanostructure family, are generally accepted to be highly inert to oxidative treatments and can only be covalently modifi ed by highly reactive species. Conversely, it is discovered that the BNNTs can be chemically dispersed and their morphology modifi ed by a relatively mild method: simply sonicating the nanotubes in aqueous ammonia solution. The dispersed nanotubes are significantly corroded, with end-caps removed, tips sharpened, and walls thinned. The sonication treatment in aqueous ammonia solution also removes amorphous BN impurities and shortened BNNTs, resembling various oxidative treatments of carbon nanotubes. Importantly, the majority of BNNTs are at least partially longitudinally cut, or "unzipped". Entangled and freestanding BN nanoribbons (BNNRs), resulting from the unzipping, are found to be approximately 5-20 nm in width and up to a few hundred nanometers in length. This is the fi rst chemical method to obtain BNNRs from BNNT unzipping. This method is not derived from known carbon nanotube unzipping strategies, but is unique to BNNTs because the use of aqueous ammonia solutions specifi cally targets the B-N bond network. This study may pave the way for convenient processing of BNNTs, previously thought to be highly inert, toward controlling their dispersion, purity, lengths, and electronic properties.

Liao, Yunlong↗
NASA NTRS2014

Sulphur-bearing Compounds Detected by MSL SAM Evolved Gas Analysis of Materials from Yellowknife Bay, Gale Crater, Mars

The Sample Analysis at Mars (SAM) and Chemistry and Mineralogy (CheMin) instruments on the Mars Science Laboratory (MSL) analysed several subsamples of sample fines (<150 μm) from three sites in Yellowknife Bay, an aeolian bedform termed Rocknest (hereafter "RN") and two samples drilled from the Sheepbed mudstone at sites named John Klein ("JK") and Cumberland ("CB"). SAM's evolved gas analysis (EGA) mass spectrometry detected H2O, CO2, O2, H2, SO2, H2S, HCl, NO, OCS, CS2 and other trace gases. The identity of evolved gases and temperature (T) of evolution can support mineral detection by CheMin and place constraints on trace volatile-bearing phases present below the CheMin detection limit or difficult to characterize with XRD (e.g., X-ray amorphous phases). Here, we focus on potential constraints on phases that evolved SO2, H2S, OCS, and CS2 during thermal analysis.

McAdam, A. C.↗
NASA NTRS2013

Comet C2012 S1 (ISON): Observations of the Dust Grains From SOFIA and of the Atomic Gas From NSO Dunn and Mcmath-Pierce Solar Telescopes

Comet C/2012 S1 (ISON) is unique in that it is a dynamically new comet derived from the Oort cloud reservoir of comets with a sun-grazing orbit. Infrared (IR) and visible wavelength observing campaigns were planned on NASA's Stratospheric Observatory For Infrared Astronomy (SOFIA) and on National Solar Observatory Dunn (DST) and McMath-Pierce Solar Telescopes, respectively. We highlight our SOFIA (+FORCAST) mid- to far-IR images and spectroscopy (approx. 5-35 microns) of the dust in the coma of ISON are to be obtained by the ISON-SOFIA Team during a flight window 2013 Oct 21-23 UT (r_h approx. = 1.18 AU). Dust characteristics, identified through the 10 micron silicate emission feature and its strength, as well as spectral features from cometary crystalline silicates (Forsterite) at 11.05-11.2 microns, and near 16, 19, 23.5, 27.5, and 33 microns are compared with other Oort cloud comets that span the range of small and/or highly porous grains (e.g., C/1995 O1 (Hale-Bopp) and C/2001 Q4 (NEAT) to large and/or compact grains (e.g., C/2007 N4 (Lulin) and C/2006 P1 (McNaught)). Measurement of the crystalline peaks in contrast to the broad 10 and 20 micron amorphous silicate features yields the cometary silicate crystalline mass fraction, which is a benchmark for radial transport in our protoplanetary disk. The central wavelength positions, relative intensities, and feature asymmetries for the crystalline peaks may constrain the shapes of the crystals. Only SOFIA can look for cometary organics in the 5-8 micron region. Spatially resolved measurements of atoms and simple molecules from when comet ISON is near the Sun (r_h< 0.4 AU, near Nov-20-Dec-03 UT) were proposed for by the ISON-DST Team. Comet ISON is the first comet since comet Ikeya-Seki (1965f) suitable for studying the alkalai metals Na and K and the atoms specifically attributed to dust grains including Mg, Si, Fe, as well as Ca. DST's Horizontal Grating Spectrometer (HGS) measures 4 settings: Na I, K, C2 to sample cometary organics (along with Mg I), and [OI] as a proxy for activity from water (along with Si I and Fe I). State-of-the-art instruments that will also be employed include IBIS, which is a Fabry-Perot spectral imaging system that concurrently measures lines of Na, K, Ca II, or Fe, and ROSA (CSUN/QUB), which is a rapid imager that simultaneously monitors Ca II or CN. From McMath-Pierce, the Solar-Stellar Spectrograph also will target ISON (320-900 nm, R approx. 21,000, r_h<0.3 AU). Assuming survival, the intent is to target ISON over r_h<0.4 AU, characteristic of prior Na detections.

Oort cloud comets↗
NASA NTRS2014

Unusual Microtopography on an Apollo 12 Soil Grain

We have observed the presence of a previously undescribed microtopography in several regions on the surface of a lunar grain from Apollo regolith sample 12070,29. This microtopography consists of flattened triangular prisms, henceforth referred to as denticles, set in an orderly arrangement. We propose three possible processes to describe the presence of these structures: (1) radiation; (2) aqueous activity; or (3) impact. Radiation—the surface of the Earth’s moon is subject to energetic ion and photon irradiation which can produce a multitude of morphological effects on grain surfaces including erosion/sputtering, vesicle formation, and amorphization of crystalline phases. Under certain conditions surface erosion can result in the formation of well-ordered nanostructures including mounds, dots, wave-shaped, rippled or corrugated features typically <10s nm in size and organized into pattered arrays. However larger pyramid-shaped features up to approx. 300 nm at the base, similar in shape to lunar denticles, were produced on Cu substrates ex-posed to ion beam sputtering.. Aqueous alteration—recent reports of purported water on the Moon imply the possibility of brief, limited exposure of surface materials to aqueous fluids. Aqueous corrosion of silicates can result in the formation of crystallographically controlled denticulated features, up to 10s of micron at the base, arranged in a patterned formation. Impact—the surface of the moon is impacted by meteorites, particularly by micron-size particles, resulting in the formation of a variety of crater types. While it is difficult to envision a scenario in which a patterned array could be formed by impact, fracturing along planes of crystallographic structural weakness due to external stress could explain these features.

Thomas-Keprta, K. L.↗
NASA NTRS2014

SAM-Like Evolved Gas Analyses of Phyllosilicate Minerals and Applications to SAM Analyses of the Sheepbed Mudstone, Gale Crater, Mars

While in Yellowknife Bay, the Mars Science Laboratory Curiosity rover collected two drilled samples, John Klein (hereafter "JK") and Cumberland ("CB"), from the Sheepbed mudstone, as well as a scooped sample from the Rocknest aeolian bedform ("RN"). These samples were sieved by Curiosity's sample processing system and then several subsamples of these materials were delivered to the Sample Analysis at Mars (SAM) instrument suite and the CheMin X-ray diffraction/X-ray fluorescence instrument. CheMin provided the first in situ X-ray diffraction-based evidence of clay minerals on Mars, which are likely trioctahedral smectites (e.g., Fe-saponite) and comprise ~20 wt% of the mudstone samples [1]. SAM's evolved gas analysis (EGA) mass spectrometry analyses of JK and CB subsamples, as well as RN subsamples, detected H2O, CO2, O2, H2, SO2, H2S, HCl, NO, OCS, CS2 and other trace gases evolved during pyrolysis. The identity of evolved gases and temperature( s) of evolution can augment mineral detection by CheMin and place constraints on trace volatile-bearing phases present below the CheMin detection limit or those phases difficult to characterize with XRD (e.g., X-ray amorphous phases). Here we will focus on the SAM H2O data, in the context of CheMin analyses, and comparisons to laboratory SAM-like analyses of several phyllosilicate minerals including smectites.

McAdam, A. C.↗
NASA NTRS2014

A Novel Hybrid Ultramicrotomy/FIB-SEM Technique: Preparation of Serial Electron-Transparent Thin Sections of a Hayabusa Grain

The Japanese space agency's (JAXA) Hayabusa mission returned the first particulate samples (typically <100micron) from the surface of an asteroid (25143 Itokawa). These precious samples provide important insights into early Solar System processes, but their sizes pose tremendous challenges to coordinated analysis using a variety of nano- and micro-beam techniques. The ability to glean maximal information from individual particles has become increasingly important and depends critically on sample preparation. We developed a hybrid technique combining traditional ultramicrotomy with focused ion beam (FIB) techniques, allowing for more thorough in situ investigations of grain surfaces and interiors. Using this method, we increase the number of FIB-prepared sections that can be recovered from a particle with dimensions on the order of tens of microns. These sections can be subsequently analyzed using a variety of analytical techniques. Particle RA-QD02-0211 is a approx. 40×40×20 micron particle from Itokawa containing olivine and Fe sulfides. It was embedded in low viscosity epoxy and partly sectioned to a depth of approx 10 micron; sections are placed on Cu grids with thin amorphous films for transmission electron microscope (TEM) analyses. With the sample surface partly exposed, the epoxy bullet is trimmed to a height of approx. 5mm to accommodate the allowable dimensions for FIB work (FEI Quanta 600 3D dual beam FIB-SEM). Using a diamond trim knife, the epoxy surrounding the grain is removed on 3 sides (to within a few microns of the grain); the depth of material removed extends well below the bottom of the particle. The sample is attached to an SEM pin mount, the epoxy coated with conductive paint, and the entire assembly coated with approx. 40nm of carbon to eliminate sample charging during FIB work. A protective carbon cap is placed according to the plan for the 15 FIB sections. The central 'spine' of the cap runs perpendicular to the front of the sample, and the 'ribs' protruding from either side run parallel. Each rib indicates the location of a planned FIB section, and the spine contains the final two planned sections. We use a cap with a 4 micron-wide spine and 2micron-wide ribs that have ≳3.5 micron of space between them (narrower cuts result in too much re-deposition of material inside the trenches). Using a 30kV, 3nA ion-beam we expose the front surface of the grain and commence milling trenches between sections. Rather than using the typical C-cut to prepare the sample for lift-out, an L-cut is used instead, leaving the sample connected by an interior tab. tab. Sections are lifted out, attached to TEM grids and thinned to electron transparency. TEM analyses show that our hybrid technique preserves both interior and edge features, including surface modifications from exposure to the space environment, such as damaged rims that form in response to solar wind implantation effects and adhering grains. In addition, the FIB sections provide larger areas that are free of fractures and chatter effects in comparison to the microtome thin sections, thus enabling more accurate measurements of solar flare particle track densities that are used to determine the surface exposure age of the particles.

Berger, Eve L.↗
NASA NTRS2014

Space Weathering of Olivine in Lunar Soils: A Comparison to Itokawa Regolith Samples

Regolith particles from airless bodies preserve a record of the space weathering processes that occurred during their surface exposure history. These processes have major implications for interpreting remote-sensing data from airless bodies. Solar wind irradiation effects occur in the rims of exposed grains, and impact processes result in the accumulation of vapordeposited elements and other surface-adhering materials. The grains returned from the surface of Itokawa by the Hayabusa mission allow the space weathering "style" of a chondritic, asteroidal "soil" to be compared to the lunar case. Here, we present new studies of space-weathered olivine grains from lunar soils, and compare these results to olivine grains from Itokawa. Samples and Methods: We analyzed microtome thin sections of olivine grains from the 20-45 micron fractions of three lunar soils: 71061, 71501 and 10084 (immature, submature and mature, respectively). Imaging and analytical data were obtained using a JEOL 2500SE 200kV field-emission scanning-transmission electron microscope equipped with a thin-window energy-dispersive x-ray spectrometer. Similar analyses were obtained from three Hayabusa olivine grains. Results and Discussion: We observed lunar grains showing a range of solar flare track densities (from <10(exp 9) to approx.10(exp 12)/sq cm). The lunar olivines all show disordered, highly strained, nanocrystalline rims up to 150-nm thick. The disordered rim thickness is positively correlated with solar flare track density. All of the disordered rims are overlain by a Si-rich amorphous layer, ranging up to 50-nm thick, enriched in elements that are not derived from the host olivine (e.g., Ca, Al, and Ti). The outmost layer represents impact-generated vapor deposits typically observed on other lunar soil grains. The Hayabusa olivine grains show track densities <10(exp 10)/sq cm and display disordered rims 50- to 100-nm thick. The track densities are intermediate to those observed in olivines in immature and submature lunar soils and indicate surface exposures of approx. 10(exp 5) years. The outermost few nanometers of the disordered rims on Hayabusa olivines are more Si-rich and Mg- and Fe-depleted relative to the cores of the grains and likely represent a minor accumulation of impact-generated vapors or sputter deposits. Nanophase Fe metal particles are less abundant in the Hayabusa rims compared to the rims on lunar grains. Conclusions: The Hayabusa and lunar olivine grain rims have widths and microstructures consistent with formation from atomic displacement damage from solar wind ions. The space weathering features in the Hayabusa grains are similar to those observed in olivines from immature to submature lunar soils. A major difference, however, is that the Hayabusa grains appear to lack the hypervelocity impact products (melt spherules, thick vapor deposits, and abundant nanophase Fe metal particles) that are common in lunar soil grains with a similar exposure history.

Keller, L. P.↗
NASA NTRS2013

The Importance of Physical Models for Deriving Dust Masses and Grain Size Distributions in Supernova Ejecta. I. Radiatively Heated Dust in the Crab Nebula

Recent far-infrared (IR) observations of supernova remnants (SNRs) have revealed significantly large amounts of newly condensed dust in their ejecta, comparable to the total mass of available refractory elements. The dust masses derived from these observations assume that all the grains of a given species radiate at the same temperature, regardless of the dust heating mechanism or grain radius. In this paper, we derive the dust mass in the ejecta of the Crab Nebula, using a physical model for the heating and radiation from the dust. We adopt a power-law distribution of grain sizes and two different dust compositions (silicates and amorphous carbon), and calculate the heating rate of each dust grain by the radiation from the pulsar wind nebula. We find that the grains attain a continuous range of temperatures, depending on their size and composition. The total mass derived from the best-fit models to the observed IR spectrum is 0.019-0.13 Solar Mass, depending on the assumed grain composition. We find that the power-law size distribution of dust grains is characterized by a power-law index of 3.5-4.0 and a maximum grain size larger than 0.1 micron. The grain sizes and composition are consistent with what is expected for dust grains formed in a Type IIP supernova (SN). Our derived dust mass is at least a factor of two less than the mass reported in previous studies of the Crab Nebula that assumed more simplified two-temperature models. These models also require a larger mass of refractory elements to be locked up in dust than was likely available in the ejecta. The results of this study show that a physical model resulting in a realistic distribution of dust temperatures can constrain the dust properties and affect the derived dust masses. Our study may also have important implications for deriving grain properties and mass estimates in other SNRs and for the ultimate question of whether SNe are major sources of dust in the Galactic interstellar medium and in external galaxies.

Importance↗
NASA NTRS2014

Paleoenvironmental Implications of Clay Minerals at Yellowknife Bay, Gale Crater, Mars

The Mars Science Laboratory (MSL) Rover, Curiosity spent approx 150 sols at Yellowknife Bay (YKB) studying a section of fluvio-lacustrine sedimentary rocks (with potential indications of volcanic influence), informally known as the Yellowknife Bay formation. YKB lies in a distal region of the Peace Vallis alluvial fan, which extends from the northern rim of Gale Crater toward the dune field at the base of Mt Sharp. Sedimentological and stratigraphic observations are consistent with the Yellowknife Bay formation being part of a distal fan deposit, which could be as young as middle Hesperian to even early Amazonian in age (approx. 3.5 to 2.5 Ga). The Yellowknife Bay formation hosts a unit of mudstone called the Sheepbed member. Curiosity obtained powdered rock samples from two drill holes in the Sheepbed Member, named John Klein and Cumberland, and delivered them to instruments in Curiosity. Data from CheMin, a combined X-ray diffraction (XRD)/X-ray fluorescence instrument (XRF), has allowed detailed mineralogical analysis of mudstone powders revealing a clay mineral component of approx. 20 wt.% in each sample. The clay minerals are important indicators of paleoenvironmental conditions and sensitive recorders of post-depositional alteration processes. The XRD pattern of John Klein reveals a 02l band consistent with a trioctahedral phyllosilicate. A broad peak at approx. 10A with a slight inflexion at approx. 12A indicates the presence of 2:1 type clay minerals in the John Klein sample. The trioctahedral nature of the clay minerals, breadth of the basal reflection, and presence of a minor component with larger basal spacing suggests that John Klein contains a trioctahedral smectite (probably saponite), whose interlayer is largely collapsed because of the low-humidity conditions. The XRD patterns show no evidence of corrensite (mixed-layer chlorite/smectite) or chlorite, which are typical diagenetic products of trioctahedral smectites when subjected to burial and heating >60 C in the presence of water. Given estimated geothermal gradients on Mars temperatures <60 C might still be consistent with (but do not require) moderate burial. However, our ability to identify interstratified minerals is greatly limited by the lack of access to traditional treatments methods used in the lab (e.g., ethylene glycol solvation). Our preferred explanation for the origin of trioctahedral smectites in Sheepbed mudstone is in situ production via reaction of olivine, water and Si-bearing amorphous material, an important mudstone component detected by XRD. Elevated levels of magnetite in the Sheepbed and the trioctahedral monomineralic nature of the clay minerals support this model. These observations, combined with previous studies of olivine stability, support the persistence of circum-neutral hydrous conditions for thousands of years at YKB.

MSL↗
NASA NTRS2014

Properties of Desert Sand and CMAS Glass

As-received desert sand from a Middle East country has been characterized for its phase composition and thermal stability. X-ray diffraction analysis showed the presence of quartz (SiO2), calcite (CaCO3), gypsum (CaSO4.2H2O), and NaAlSi3O8 phases in as-received desert sand and showed weight loss of approx. 35 percent due to decomposition of CaCO3 and CaSO4.2H2O when heated to 1400 C. A batch of as-received desert sand was melted into calcium magnesium aluminosilicate (CMAS) glass at approx. 1500 C. From inductively coupled plasma-atomic emission spectrometry, chemical composition of the CMAS glass was analyzed to be 27.8CaO-4MgO-5Al2O3-61.6SiO2-0.6Fe2O3-1K2O (mole percent). Various physical, thermal and mechanical properties of the glass have been evaluated. Bulk density of CMAS glass was 2.69 g/cc, Young's modulus 92 GPa, Shear modulus 36 GPa, Poisson's ratio 0.28, dilatometric glass transition temperature (T (sub g)) 706 C, softening point (T (sub d)) 764 C, Vickers microhardness 6.3 +/- 0.4 GPa, indentation fracture toughness 0.75 +/- 0.15 MPa.m (sup 1/2), and coefficient of thermal expansion (CTE) 9.8 x 10 (exp -6)/degC in the temperature range 25 to 700 C. Temperature dependence of viscosity has also been estimated from various reference points of the CMAS glass using the Vogel-Fulcher-Tamman (VFT) equation. The glass remained amorphous after heat treating at 850 C for 10 hr but crystallized into CaSiO3 and Ca-Mg-Al silicate phases at 900 C or higher temperatures. Crystallization kinetics of the CMAS glass has also been investigated by differential thermal analysis (DTA). Activation energies for the crystallization of two different phases in the glass were calculated to be 403 and 483 kJ/mol, respectively.

Desert sand↗
NASA NTRS2014

Additive Construction using Basalt Regolith Fines

Planetary surfaces are often covered in regolith (crushed rock), whose geologic origin is largely basalt. The lunar surface is made of small-particulate regolith and areas of boulders located in the vicinity of craters. Regolith composition also varies with location, reflecting the local bedrock geology and the nature and efficiency of the micrometeorite-impact processes. In the lowland mare areas (suitable for habitation), the regolith is composed of small granules (20 - 100 microns average size) of mare basalt and volcanic glass. Impacting micrometeorites may cause local melting, and the formation of larger glassy particles, and this regolith may contain 10-80% glass. Studies of lunar regolith are traditionally conducted with lunar regolith simulant (reconstructed soil with compositions patterned after the lunar samples returned by Apollo). The NASA Kennedy Space Center (KSC) Granular Mechanics & Regolith Operations (GMRO) lab has identified a low fidelity but economical geo-technical simulant designated as Black Point-1 (BP-1). It was found at the site of the Arizona Desert Research and Technology Studies (RATS) analog field test site at the Black Point lava flow in adjacent basalt quarry spoil mounds. This paper summarizes activities at KSC regarding the utilization of BP-1 basalt regolith and comparative work with lunar basalt simulant JSC-1A as a building material for robotic additive construction of large structures. In an effort to reduce the import or in-situ fabrication of binder additives, we focused this work on in-situ processing of regolith for construction in a single-step process after its excavation. High-temperature melting of regolith involves techniques used in glassmaking and casting (with melts of lower density and higher viscosity than those of metals), producing basaltic glass with high durability and low abrasive wear. Most Lunar simulants melt at temperatures above 1100 C, although melt processing of terrestrial regolith at 1500 C is not uncommon. These temperatures are achievable by laser heating or by using solar concentrators. Similar to volcanic magma, the cooling rate determines the crystallite size - slower cooling develops larger crystals, and rapid quenching can result in fully amorphous glass.

Additive↗
NASA NTRS2015

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.↗
NASA NTRS2015

Isotopic Composition of Carbon Dioxide Released from Confidence Hills Sediment as Measured by the Sample Analysis at Mars (SAM) Quadrupole Mass Spectrometer

In October 2014, the Mars Science Laboratory (MSL) "Curiosity" rover drilled into the sediment at the base of Mount Sharp in a location namsed Cionfidence Hills (CH). CH marked the fifth sample pocessed by the Sample Analysis at Mars (SAM) instrument suite since Curiosity arrived in Gale Crater, with previous analyses performed at Rocknest (RN), John Klein (JK), Cumberland (CB), and Windjana (WJ). Evolved gas analysis (EGA) of all samples has indicated H2O as well as O-, C- and S-bearing phases in the samples, often at abundances that would be below the detection limit of the CheMin instrument. By examining the temperatures at which gases are evolved from samples, SAM EGA data can help provide clues to the mineralogy of volatile-bearing phases when their identities are unclear to CheMin. SAM may also detect gases evolved from amorphous material in solid samples, which is not suitable for analysis by CheMin. Finally, the isotopic composition of these gases may suggest possible formation scenarios and relationships between phases. We will discuss C isotope ratios of CO2 evolved from the CH sample as measured with SAM's quadrupole mass spectrometer (QMS) and draw comparisons to samples previously analyzed by SAM.

Franz, H. B.↗
NASA NTRS2015

Crystallization Kinetics of Calcium-magnesium Aluminosilicate (CMAS) Glass

The crystallization kinetics of a calcium-magnesium aluminosilicate (CMAS) glass with composition relevant for aerospace applications, like air-breathing engines, were evaluated using differential thermal analysis (DTA) in powder and bulk forms. Activation energy and frequency factor values for crystallization of the glass were evaluated. X-ray diffraction (XRD) was used to investigate the onset of crystallization and the phases that developed after heat treating bulk glass at temperatures ranging from 690 to 960 deg for various times. Samples annealed at temperatures below 900 deg remained amorphous, while specimens heat treated at and above 900 deg exhibited crystallinity originating at the surface. The crystalline phases were identified as wollastonite (CaSiO3) and aluminum diopside (Ca(Mg,Al) (Si,Al)2O6). Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) were employed to examine the microstructure and chemical compositions of crystalline phases formed after heat treatment.

X-ray diffraction (XRD)↗