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Spectral, Compositional, and Physical Properties of the Upper Murray Formation and Vera Rubin Ridge, Gale Crater, Mars

During 2018 and 2019, the Mars Science Laboratory Curiosity rover investigated the chemistry, morphology, and stratigraphy of Vera Rubin ridge (VRR). Using orbital data from the Compact Reconnaissance Imaging Spectrometer for Mars, scientists attributed the strong 860 nm signal associated with VRR to the presence of red crystalline hematite. However, Mastcam multispectral data and CheMin X-ray diffraction (XRD) measurements show that the depth of the 860 nm absorption is negatively correlated with the abundance of red crystalline hematite, suggesting that other mineralogical or physical parameters are also controlling the 860 nm absorption. Here, we examine Mastcam and ChemCam passive reflectance spectra from VRR and other locations to link the depth, position, and presence or absence of iron-related mineralogic absorption features to the XRD-derived rock mineralogy. Correlating CheMin mineralogy to spectral parameters showed that the ~860 nm absorption has a strong positive correlation with the abundance of ferric phyllosilicates. New laboratory reflectance measurements of powdered mineral mixtures can reproduce trends found in Gale crater. We hypothesize that variations in the 860 nm absorption feature in Mastcam and ChemCam observations of VRR materials are a result of three factors: (1) variations in ferric phyllosilicate abundance due to its ~800–1,000 nm absorption; (2) variations in clinopyroxene abundance because of its band maximum at ~860 nm; and (3) the presence of red crystalline hematite because of its absorption centered at 860 nm. We also show that relatively small changes in Ca-sulfate abundance is one potential cause of the erosional resistance and geomorphic expression of VRR.

58 GEOSCIENCES↗

Pink Spinel in Apollo Impact Melt Rock 68815: Implications for Mg-Suite Magmatism

Introduction: Magnesian rocks from the lunar highlands are collectively termed the Mg-suite. Characterized by high (>60) Mg# (molar 100×Mg/[Mg+Fe]) in mafic phases and calcic plagioclase, these rocks are plutonic to hypabyssal in origin, and include a range of bulk mineralogies such as troctolites, dunites, norites, gabbronorites, and spinel troctolites [1]. These Mg-suite lithologies have distinct trace element concentrations and ratios that differentiate them from other lunar rock types. These rocks are ancient, generally dated to between 4.5 and 4.1 Ga, although it is unknown if this represents the full range of Mg-suite ages [1–2]. Among the Mg-suite lithologies, the spinel troctolites are relatively rare, to date only found in polymict breccias [3]. Spinel troctolites, as their name suggests, consist of calcic plagioclase and forsteritic olivine, with minor amounts of spinel (MgAl2O4), ± pyroxene and cordierite [1,4]. This form of spinel is often called ‘pink’ spinel because of its appearance in thin section under plane polarized light (PPL; Fig. 1), due to minor amounts of Cr. Spinel troctolites are generally plutonic or hypabyssal in origin (subsequently exhumed and incorporated into polymict breccias), or formed through impact processes (e.g., crystalline impact melt) [5]. A spinel-rich lithology has also been found in the Moscoviense region of the Moon via the Moon Mineralogy Mapper (M3) and lacks other mafic phases [6]. Finally, while the Mg-suite sampled thus far consists of plutonic (or hypabyssal) rocks, the question remains if such magmas could have erupted on the surface of the Moon [7]. These magmas have much lower density than mare basalts, but little sample or remote sensing evidence has been found to support the idea that extrusive Mg-suite volcanism occurred [7]. Here, we present a coordinated microanalytical study of spinel-bearing lithic and mineral clasts found in Apollo sample 68815. These data will be used to understand their petrogenesis (magmatic or impact) and modification histories, and to shed light on the existence of volcanic Mg-suite rocks. Sample Description: Apollo sample 68815 is a polymict impact melt breccia containing a variety of lithic and mineral fragments embedded in devitrified impact melt. This sample was chipped off the top of a boulder at Station 8 during the Apollo 16 mission and had an original weight of nearly 1.8 kg. In this study, we investigated two polished thin sections of 68815: 68815,17 and 68815,148, both containing spinel. Methods: The thin sections of 68815 were studied using optical light microscopy (PPL, cross-polarized light, and reflected light) with a Keyence VHX-7100 Digital Microscope. Each section was then X-ray mapped for 13–14 elements using a Cameca SX100 electron probe microanalyzer (EPMA) located in the Kuiper Materials Imaging and Characterization Facility (KMICF) at the University of Arizona. We have obtained geochemical information about the phases (olivine, plagioclase, spinel, pyroxene) in the thin sections also using the EPMA. In addition, we have used ThermoScientific Helios NanoLab 660 Focused-Ion-Beam Scanning-Electron Microscope (FIB-SEM) and a Hitachi S-4800 SEM (both in KMICF) to obtain backscattered electron (BSE) images and energy dispersive Xray spectrometry (EDS) maps of areas of interest. Using a JEOL 7900F SEM at the Astromaterials Research & Exploration Science (ARES) at NASA Johnson Space Center (JSC), we have obtained electron backscatter diffraction (EBSD) maps of the spinel-bearing portions of the thin sections. The EBSD data were collected under beam conditions of 20 kV, and ~90 μA, with step sizes varying from 0.05 to 2 μm. Following EBSD data collection, we processed the data using AZtecCrystal and MTEX, a free MATLAB toolbox. Results: We have found clasts with subophitic textures, that consist of primarily olivine and plagioclase, with minor amounts of pink Mg-Al spinel and pyroxene (Fig. 1). These clasts are up to ~1 mm in length and contain spinels up to 50 μm across. We have additionally identified pink Mg-Al spinels within the impact melt (i.e., not contained in lithic clasts) in both thin sections. In one instance, a single spinel grain is approximately 300 μm across (Fig. 1b, 2). The spinel fragments embedded in impact melt have varying compositions, typically distinct from the compositions of spinels in the lithic clasts. Spinel-Bearing Clasts: Ten lithic clasts with similar textures and mineral compositions were identified between 68815,17 (two clasts) and ,148 (eight clasts). These clasts fall into two groups. The first has skeletal olivine with intergranular plagioclase, with minor amounts of pyroxene and spinel (Fig. 1a, 2c, 2d). The spinel in these clasts are found amid the plagioclase. The second group have an intergranular texture of olivine and plagioclase, again with minor spinel and pyroxene. The second group may contain spinels surrounded by plagioclase, and spinels enclosed in olivine. Spinels located within both clast types range from no apparent Cr zoning, to reverse zoning (Cr-enrichment inward; Fig. 2d), to normal zoning (Cr-enrichment outward). In the clasts thus far investigated with EPMA, plagioclase compositions range from An# (molar 100×Ca/[Ca+Na+K]) 92–96. Olivine Mg# ranged from 77 to 94, while pyroxene had Mg# from 54–84. Spinel in the clasts have Cr# (molar 100×Cr/[Cr+Al]) 2–4 and Mg# 88–91, which is within the range of pristine and plutonic spinel troctolites [8]. Isolated Spinels: These crystals are generally euhedral to subhedral, and can exhibit reverse Cr zoning (Cr enrichment inward) or no apparent Cr zoning. The spinels thus far investigated via EPMA have Cr# 9–14 and Mg# 65–82. The Cr# for these spinels is within the range reported by [8], but have lower Mg#. Future Work: We will continue to process the EBSD data for these lithic and mineral clasts. We will also continue to characterize these clasts using EPMA and SEM. By thoroughly characterizing the various spinels and spinel-bearing clasts, we aim to constrain the petrogenesis of these minerals and rock fragments. Acknowledgments: We thank NASA for the loan of these thin sections. We thank Ken Domanik and Jerry Chang for their support with data collection. Work was supported by a University of Arizona RII Core Facilities Pilot Program grant and start-up funds to JJB. We acknowledge support from NASA’s Planetary Science Research program for analysis performed at JSC. References: [1] Shearer C. K. et al. (2015) Am. Min. 100, 294–325. [2] Borg L. E. et al. (2020) GCA 290, 312–332. [3] Warren P. H. (1993) Am. Min. 78, 360–376. [4] Dymek R. F. et al. (1976) LPS VII, 2335–2378. [5] Treiman et al. (2019) Am. Min. 104, 370–384. [6] Pieters et al. (2011) JGR: Plan. 116:E00G08. [7] Prissel et al. (2016) Icarus 277, 319–329. [8] Prissel et al. (2016) Am. Min. 101, 1624–1635.

spinel↗

The Rio Tinto Basin, Spain: Mineralogy, Sedimentary Geobiology, and Implications for Interpretation of Outcrop Rocks at Meridiani Planum, Mars

Exploration by the NASA rover Opportunity has revealed sulfate- and hematite-rich sedimentary rocks exposed in craters and other surface features of Meridiani Planum, Mars. Modern, Holocene, and Plio-Pleistocene deposits of the Rio Tinto, southwestern Spain, provide at least a partial environmental analog to Meridiani Planum rocks, facilitating our understanding of Meridiani mineral precipitation and diagenesis, while informing considerations of martian astrobiology. Oxidation, thought to be biologically mediated, of pyritic ore bodies by groundwaters in the source area of the Rio Tinto generates headwaters enriched in sulfuric acid and ferric iron. Seasonal evaporation of river water drives precipitation of hydronium jarosite and schwertmannite, while (Mg,Al,Fe(sup 3+))-copiapite, coquimbite, gypsum, and other sulfate minerals precipitate nearby as efflorescences where locally variable source waters are brought to the surface by capillary action. During the wet season, hydrolysis of sulfate salts results in the precipitation of nanophase goethite. Holocene and Plio-Pleistocene terraces show increasing goethite crystallinity and then replacement of goethite with hematite through time. Hematite in Meridiani spherules also formed during diagenesis, although whether these replaced precursor goethite or precipitated directly from groundwaters is not known. The retention of jarosite and other soluble sulfate salts suggests that water limited the diagenesis of Meridiani rocks. Diverse prokaryotic and eukaryotic microorganisms inhabit acidic and seasonally dry Rio Tinto environments. Organic matter does not persist in Rio Tinto sediments, but biosignatures imparted to sedimentary rocks as macroscopic textures of coated microbial streamers, surface blisters formed by biogenic gas, and microfossils preserved as casts and molds in iron oxides help to shape strategies for astrobiological investigation of Meridiani outcrops.

Fernandez-Remolar, David C.↗

Ortho and para-armalcolite samples in Apollo 17.

Two paragenetically contrasting forms of armalcolite are present in basalts from the Apollo 17 Taurus-Littrow landing site. These armalcolites differ in optical properties, in crystal habit and in their distribution between coarse and fine grained rocks. It is proposed to call the two armalcolite forms ortho-armalcolite and para-armalcolite. Texural relationships and the evidence of experimental melting show that ortho-armalcolite is always the first crystalline phase to appear from unusually titanium rich magmas. The origin of para-armalcolite is not yet fully understood.

Haggerty, S. E.↗

Mitigation of spatial nonstationarity with vision transformers

Spatial nonstationarity, the location variance of features’ statistical distributions, is ubiquitous in many natural settings. For example, in geological reservoirs rock matrix porosity varies vertically due to geomechanical compaction trends, in mineral deposits grades vary due to sedimentation and concentration processes, in hydrology rainfall varies due to the atmosphere and topography interactions, and in metallurgy crystalline structures vary due to differential cooling. Conventional geostatistical modeling workflows rely on the assumption of stationarity to be able to model spatial features for geostatistical inference. Nevertheless, this is often not a realistic assumption when dealing with nonstationary spatial data and this has motivated a variety of nonstationary spatial modeling workflows such as trend and residual decomposition, cosimulation with secondary features, and spatial segmentation and independent modeling over stationary subdomains. The advent of deep learning technologies has enabled new workflows for modeling spatial relationships. However, there is a paucity of demonstrated best practice and general guidance on mitigation of spatial nonstationarity with deep learning in the geospatial context. We demonstrate the impact of two common types of geostatistical spatial nonstationarity on deep learning model prediction performance and propose the mitigation of such impacts using self-attention (vision transformer) models. We demonstrate the utility of vision transformers for the mitigation of nonstationarity with relative errors as low as 10%, exceeding the performance of alternative deep learning methods such as convolutional neural networks. We establish best practice by demonstrating the ability of self-attention networks for modeling large-scale spatial relationships in the presence of commonly observed geospatial nonstationarity.

58 GEOSCIENCES↗

Ordovician impacts at sea in Baltoscandia

Northern Europe has an assemblage of Ordovician probable impacts that is exceptional because the structures involved are relatively old yet well preserved because they formed at sea and because they formed within a restricted geological time in a relatively small area. The Tvaren, Kardla, and Lockne structures might not be strictly contemporaneous but all formed near the beginning of the Caradoc Age (about 460 Ma), whereas the Granby structure is about 20 Ma older. The range of diameters is from about 2 km (Tvaren, Granby) to 8 km (Lockne). The stratigraphic succession formed on impact at sea, as uniformly documented by these structures, begins with a breccia lens consisting of basement rocks that are intensely crushed. Owing to expulsion of sea water by the impact, this breccia formed under essentially dry conditions. Later on this breccia was in part hydrothermally altered. It is overlain by backsurge turbidite that formed from fragments of local sedimentary bedrock and crystalline basement when the sea water returned to the crater site. Either the turbidite is simply a Bouma sequence (although quite thick - as much as over 50 m) from very coarse rubble to mud, or it is more complex. After deposition of the backsurge turbidite, or turbidite complex, the craters still remained as 150-200-m-deep holes in the sea bed. Together with the presence of relatively shallow water over the rim wall, this situation created predictable hydrologic conditions for extended histories of sedimentation and biological development at the crater as well as within it. The presence of a concentration of craters within a limited area of well-preserved and accessible Ordovician deposits raises a question about the Ordovician, especially its middle portion, as potentially an age of relatively intense impact activity even in wider areas. In this connection it may be apposite to mention that the only fossil stony meteorites so far recorded in rocks are from the late Early and the Middle Ordovician.

Lindstroem, M.↗

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

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

Smith, R. J.↗

Mineralogy of Rock Flour in Glaciated Volcanic Terrains: An Analog for a Cold and Icy Early Mars

Geomorphological and mineralogical data from early Martian surfaces indicate liquid water was present on ancient Mars. The relative surface temperatures, however, remain a subject of debate. Was early Mars warm and wet or cold and icy with punctuated periods of warmth and ice melt? By characterizing the mineralogy and geochemistry of modern icy mafic terrains on Earth, we can search for these characteristics in early Martian terrains to better constrain the early Martian climate. Here, we describe the mineralogy of glacial flour in a modern glaciated volcanic terrain in Oregon, USA. We are particularly interested in secondary phases that form in these environments, and we hypothesize that poorly crystalline phases may preferentially form in these terrains because of the low temperatures and the seasonality of melt water production. A description of the mineralogy of the moraines, the composition of the amorphous materials, and the geochemistry of the glacial melt waters are presented elsewhere. Glacial flour is made up of silt- and clay-sized particles that form from the physical weathering of rock underlying a wet-based glacier as the glacier slides over it. Flour is usually transported from underneath a glacier by melt water streams. The geochemistry of glacial melt water streams has been studied extensively and has been used to infer weathering reactions within glacial systems. However, the mineralogy of these environments, especially on mafic volcanic terrains, is not well studied. Rock flour is a ubiquitous physical weathering product in glaciated terrains and, therefore, affects microbial habitats, stream and lake chemistry, and chemical weathering processes. and by studying the mineralogy of glacial flour, we can better understand geochemical and microbiological processes in subglacial and proglacial terrains.

Rampe, E. B.↗

Ferroelectric Al1 − xBxN thin films integrated on Si

Ferroelectric Al0.93B0.07N thin films are prepared (100) Si substrates. The necessary c-axis out-of-plane orientation to observe macroscopic ferroelectric switching was achieved by implementing an initial Ar/N2 plasma treatment, followed by a thin layer of AlN to initiate the desired texture and a 150 nm W layer. The plasma treatment facilitates crystallinity enhancement of the AlN template layer, allowing for subsequent growth of highly oriented W and Al0.93B0.07N layers. The W layer exhibits random in-plane orientation and exclusive (110) out-of-plane orientation with a rocking curve width of 1.4°. When grown on these W surfaces, 175 nm thick Al0.93B0.07N films exhibit random in-plane orientation and exclusive (001) texture with rocking curve full-width-half-max values of 1.6° and RMS roughness values less than 1 nm. Polarization hysteresis measurements show robust hysteresis with coercive field values of 5.4 MV/cm and remanent polarization values of 136 μC/cm2. XPS depth profile analysis suggests that the plasma treatment converts the existing native oxide to a nitrogen rich oxynitride with approximate composition Si3O0.5N3.67. Cross-sectional TEM reveals that the oxynitride interlayer is amorphous and ∼3.4 nm thick, more than double the native oxide thickness measured by multiwavelength ellipsometry, implying that (oxy)nitride growth continues after conversion of the native oxide. This new family of ferroelectric wurtzites is interesting from an integration perspective given their chemical compatibility with mainstream semiconductors. Developing synthesis routes that promote needed texture while preserving compatible processing windows is an important step toward practical integration.

Physics↗

Overview and Initial Results of SAND-E: Semi-Autonomous Navigation for Detrital Environments

Unmanned aerial systems (UAS) and automated terrain analysis for science and navigation are new technologies for planetary exploration. The Mars Helicopter will fly with the Mars2020 rover, the Dragonfly quadcopter will explore Titan, and Soil Properties and Object Classification (SPOC) software will be used for path planning and navigation on the Mars2020 rover. Using an Argo J5 rover instrumented with stereo cameras and Autonomous Soil Assessment System (ASAS) software, and an off the shelf quadcopter, SAND-E tested the use of automated terrain analysis and UAS data for science operations in a Mars-analog environment in Iceland during July of 2019. Scientifically, we sought to determine changes in the physical and chemical properties of sediments along a glacial-fluvial-aeolian transport pathway. Operationally, we tested rover mission-like scenarios that included UAS images and classified terrain images. Here, we present the initial results for both the operations and science elements of the study. Site Selection: A goal of SAND-E is examine sorting and alteration of sediments in fluvial and aeolian environments in both mineral-dominated and glass-dominated basaltic settings. During the first year of the project we focused on a mineral-dominated environment. Selection of the location was based on prior publications that indicated our selected region had a greater abundance of crystalline sediments than other areas fluvial-aeolian settings in Iceland. Other criteria included the presence of both fluvial and aeolian landforms along a transport pathway such that the sediments in transport could be linked to their source rocks. We chose the Skjaldbreidauhraun glacial outwash plain, which sits at the base of Thórisjökull glacier. The site is 30 km north of Thingvellir National Park and ~2 hours from Reykjavik. The outwash plain is fed by two small catchments that drain from the base of the glacier and cut through hyaloclastite and shield volcano bedrock. The drainage progresses from steep alluvial fans near the glacier into a low-sloping fluvial braidplain that becomes confined by the Skjaldbreidur shield volcano and creates a shallow canyon cut into lava bedrock. The fluvial system was a typical braided alluvial environment composed pebble- and cobble-bedded longitudinal bars and sandy channel beds. The river remained active and fluctuated in response to diurnal runoff cycles near the glacier before disappearing into the sandy substrate downstream. The high concentration of suspended sediment in the river was evident by the cloudy water and the silt and clay-sized sediments that draped the channel beds after abandonment and created playas in the lowest sloping areas of the catchment. The entire fluvial system was affected by the winds generated by frontal systems and katabatic flows descending the glacier. This resulted in the formation of aeolian lag deposits and a wind-deflation plain where the fluvial system was not active. Wind ripples and drifts formed in abandoned fluvial channels from aeolian reworking of the sand-sized fluvial sediments. The silt- and clay-sized sediments found in fluvial channels, bar tops, and playas generated dust plumes during high wind events. Our operation sought to capture the variability in this system by sampling from the range of fluvial and aeolian features 6.3 km (proximal), 11.3 km (medial), and 14.4 km (distal) along the river from its origin at the base of glacier.

Ewing, R. C.↗

Equilibrium studies with a bearing on lunar rocks.

Review of the results of equilibrium studies of lunar rocks and of synthesized oxide and silicate phases performed in the temperature range from 1000 to 1400 C under strongly reducing conditions of a total pressure of 1 atm. Determined liquidus and solidus temperatures and sequence of appearance of crystalline phases are presented. The studies of synthesized mixtures are concentrated in two main areas, one dealing with subsolidus relations in titanate and spinel phases, the other with liquidus phase relations in simplified iron silicate systems.

Muan, A.↗

Concerning the meteoritic origin of the Puchezh-Katunki crater

Criticism of the works of Vardaniants (1961) and Goretskii (1962) regarding the origin of the Puchezh-Katunki crater, and development of a new hypothesis regarding this disturbance. Although Vardaniants defines the Puchezh-Katunki disturbance as a structure of explosive nature and assumes that the explosion originated as a consequence of accumulation of gases in the crystalline basement of the Russian platform, he lacks evidence to qualify this explosion as coming from a depth. Goretskii's tectonic-injection hypothesis attributes the formation of the disturbance to penetration of an intrusion of basic and ultrabasic rocks into the Paleozoic rocks of the platform. It is shown that, even if the intrusion were spread somewhere at depth, it could not account for the extent of the deformation in the disturbance. It is suggested that this disturbance is of meteoritic origin, since the structure and morphology of the region are similar to the sloping conical surface produced by an explosive meteor crater. The energy, mass, and size of the asteroid which could cause such a disturbance are estimated, and it is shown that the probability of the occurrence of an impact of this size is finite over geological time.

Firsov, L.↗

Petrology of Luna 20 regolith from the lunar highlands.

The Luna 20 regolith sample contains crystalline lithic fragments of mare basalt, the anorthosite-norite-troctolite group, and feldspathic basalt. Discrete mineral fragments and mineral fragments in regolith breccias can generally be assigned, based on chemical criteria, to one or the other of the first two rock types. A complex history is indicated for the regolith fragments involving repeated metamorphism and melting of the highlands due to impact events. The glass fragments and the feldspathic basalts probably are the result of this melting and their composition may be representative of a large portion of the regolith at this site.

Crawford, M. L.↗

Dynamic crystallization of silicate melts

Two types of furnaces with differing temperature range capabilities were used to provide variations in melt temperatures and cooling rates in a study of the effects of heterogeneous nucleation on crystallization. Materials of chondrule composition were used to further understanding of how the disequilibrium features displayed by minerals in rocks are formed. Results show that the textures of natural chondrules were duplicated. It is concluded that the melt history is dominant over cooling rate and composition in controlling texture. The importance of nuclei, which are most readily derived from preexisting crystalline material, support an origin for natural chondrules based on remelting of crystalline material. This would be compatible with a simple, uniform chondrule forming process having only slight variations in thermal histories resulting in the wide range of textures.

Russell, W. J.↗

Epitaxial Ferroelectric Ba(0.5)Sr(0.5)TiO3 Thin Films for Room-Temperature High-Frequency Tunable Element Applications

Perovskite Ba(0.5)SR(0.5)TiO3 thin films have been synthesized on (001) LaAl03 substrates by pulsed laser ablation. Extensive X-ray diffraction, rocking curve, and pole-figure studies suggest that the films are c-axis oriented and exhibit good in-plane relationship of <100>(sub BSTO)//<100>(sub LAO). Rutherford Backscattering Spectrometry studies indicate that the epitaxial films have excellent crystalline quality with an ion beam minimum yield chi(sub min) Of only 2.6 %. The dielectric property measurements by the interdigital technique at 1 MHz show room temperature values of the relative dielectric constant, epsilon(sub r), and loss tangent, tan(sub delta), of 1430 and 0.007 with no bias, and 960 and 0.001 with 35 V bias, respectively. The obtained data suggest that the as-grown Ba(0.5)SR(0.5)TiO3 films can be used for development of room-temperature high-frequency tunable elements.

Chen, C. L.↗

A Solar System Perspective on Laboratory Astrophysics

Planetary science deals with a wide variety of natural materials in a wide variety of environments. These materials include metals, minerals, ices, gases, plasmas, and organic chemicals. In addition, the newly defined discipline of astrobiology introduces biological materials to planetary science. The environments range from the interiors of planets with megapascal pressures to planetary magnetospheres, encompassing planetary mantles, surfaces, atmospheres, and ionospheres. The interplanetary environment includes magnetic and electrical fields, plasma, and dust. In order to understand planetary processes over these vast ranges, the properties of materials must be known, and most of the necessary information comes from the laboratory. Observations of the bodies and materials in the Solar System are accomplished over the full range of the electromagnetic spectrum by remote sensing from Earth or spacecraft. Comets exemplify this; molecular and atomic identifications are made from the hard ultraviolet to radio wavelengths, while X-rays are emitted as comets interact with the solar wind. Gamma rays from the surfaces of the Moon and asteroids are diagnostic of the mineral and ice content of those bodies; eventually, gamma rays will also be observed by probes to comets. A number of planetary materials are available in the laboratory for extensive Study: rocks from the Moon, Mars, several asteroids, as well as dust from comets (and perhaps the Kuiper Belt) are closely studied at every level, including atomic (isotopic). Even pre-solar interstellar grains isolated from meteorites are scrutinized for composition and crystalline structure. Beyond the materials themselves, various agents and processes have altered them over the 4.6-Gy age of the Solar System. Solar radiation, solar wind particles, trapped magnetospheric particles, cosmic rays, and micrometeoroid impacts have produced chemical, physical, and morphological changes in the atmospheres and on the surfaces of all planetary bodies. These processes are not well understood, so studies in a laboratory setting are especially needed.

Cruikshank, Dale P.↗

Some things we can infer about the Moon from the Composition of the Apollo 16 Regolith

Characteristics of the regolith of Cayley plains as sampled at the Apollo 16 lunar landing site are reviewed and new compositional data are presented for samples of less than 1 mm fines ('soils') and 1-2 mm regolith particles. As a means of determining which of the many primary (igneous) and secondary (crystalline breccias) lithologic components that have been identified in the soil are volumetrically important and providing an estimate of their relative abundances, more than 3 x 10(exp 6) combinations of components representing nearly every lithology that has been observed in the Apollo 16 regolith were systematically tested to determine which combinations best account for the composition of the soils. Conclusions drawn from the modeling include the following. At the site, mature soil from the Cayley plains consists of 64.5% +/- 2.7% components representing 'prebasin' materials: anorthosites, feldspathic breccias, and a small amount (2.6% +/- 1.5% of total soil) of nonmare, mafic plutonic rocks, mostly gabbronorites. On average, these components are highly feldspathic, with average concentrations of 3l-32% Al2O3 and 2-3% FeO and a molar Mg/(Mg+Fe) ratio of O.68. The remaining 36% of the regolith is syn- and postbasin material: 28.8% +/- 2.4% mafic impact-melt breccias (MIMBS, i.e., 'LKFM' and 'VHA basalts') created at the time of basin formation, 6.0% +/- 1.4% mare-derived material (impact and volcanic glass, crystalline basalt) with an average TiO2 concentration of 2.4%, and 1% postbasin meteoritic material. The MIMBs are the principal (80-90%) carrier of incompatible trace elements (rare earths, Th, etc.) and the carrier of about one-half of the siderophile elements and elements associated with mafic mineral phases (Fe, Mg, Mn, Cr, Sc). Most (71 %) of the Fe in the present regolith derives from syn- and postbasin sources (MIMBS, mare-derived material, and meteorites). Thus, although the bulk composition of the Apollo 16 regolith is nominally that of noritic anorthosite, the noritic part (the MIMBs) and anorthositic parts (the prebasin components) are largely unrelated.

Korotev, Randy L.↗

Effects of Extended Aqueous Processing on Structure, Chemistry, and Performance of Polycrystalline LiNi x Mn y Co z O 2 Cathode Powders

The prospect of aqueous processing of LiNi x Mn y Co z O 2 (NMC) cathodes has significant appeal to battery manufacturers for the reduction in materials cost, toxicological risk, and environmental impact compared to conventional N -methyl-2-pyrrolidone (NMP)-based processing. However, the effects of aqueous processing of NMC powders at industrial timescales are not well studied, with prior studies mostly focusing on relatively brief water washing processes. Here, we investigate the bulk and surface impacts of extended aqueous processing of polycrystalline NMC powders with different compositions. We demonstrate that at timescales of several hours, polycrystalline NMC is susceptible to intergranular fracture, with the severity of fracture scaling with the NMC nickel content. While bulk crystallinity and composition are unchanged, surface sensitive techniques such as X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) indicate that the exposure of water leads to a level of delithiation, nickel reduction, and reconstruction from the layered to rock-salt structure at the surface of individual grains. Dynamic single NMC microparticle compression testing suggests that the resulting mechanical stresses weaken the integrity of the polycrystalline particle and increases susceptibility of intergranular fracture. The initially degraded surfaces along with the increased surface area lead to faster capacity fade and impedance growth during electrochemical cycling. From this work, it is demonstrated that NMC powders require surface or grain boundary modifications to make industrial-scale aqueous cathode processing viable, especially for next-generation nickel-rich NMC chemistries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗