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At least 379 records · Page 21

Carbonaceous Components in the Comet Halley Dust

Cometary grains containing large amounts of carbon and/or organic matter (CHON) were discovered by in situ measurements of comet Halley dust composition during VEGA and GIOTTO flyby missions. In this paper, we report the classification of these cometary, grains by means of cluster analysis, discuss the resulting compositional groups, and compare them with substances observed or hypothesized in meteorites, interplanetary dust particles, and the interstellar medium. Grains dominated by carbon and/or organic matter (CHON grains) represent approx. 22% of the total population of measured cometary dust particles. They, usually contain a minor abundance of rock-forming elements as well. Grains having organic material are relatively more abundant in the vicinity of the nucleus than in the outer regions of the coma, which suggests decomposition of the organics in the coma environment. The majority of comet Halley organic particles are multicomponent mixtures of carbon phases and organic compounds. Possibly, the cometary CHON grains may be related to kerogen material of an interstellar origin in carbonaceous meteorites. Pure carbon grains, hydrocarbons and polymers of cyanopolyynes, and multi-carbon monoxides are present in cometary dust as compositionally simple and distinctive components among a variety of others. There is no clear evidence of significant presence of pure formaldehyde or HCN polymers in Halley dust particles. The diversity of types of cometary organic compounds is consistent with the inter-stellar dust model of comets and probably reflects differences in composition of precursor dust. Preservation of this heterogeneity among submicron particles suggest the gentle formation of cometary, nucleus by aggregation of interstellar dust in the protosolar nebula without complete mixing or chemical homogenization at the submicron level.

Fomenkova, M. N.↗

Anomalous and Ungrouped Carbonaceous Chondrites in the US Antarctic Meteorite Collection and their Potential Relevance to Ryugu and Bennu

With two different carbonaceous asteroid sample return missions in full swing, attention has focused on what connections can be made between the asteroid samples and the wide range of carbonaceous chondrite meteorites in worldwide collections. The US Antarctic meteorite collection contains nearly 1000 carbonaceous chondrites of various types including many in well-established groups as well as ungrouped, unusual or anomalous groups [1]. Some of the latter have been included in, or are possibly related to, recently proposed new carbonaceous chondrite classifications – CA and CY chondrites [2,3]. In addition to these, there are numerous ungrouped samples that have properties intermediate between established groups (like CM and CO; [4]), distinct from any other groups [5], or have anomalous properties that might be attributable to parent body processes such as heating, fluid interaction, or impacts [6]. Some CM anomalous or ungrouped chondrites share spectral features with Ryugu, which has a small hydration peak arguably due to hydrated minerals left after either impact heating or shock in carbonaceous chondrites [7]. PCA 91008, PCA 02012, GRO 95566, and LEW 85311 are all CMs that have experienced heating or metamorphism that may be due to impacts, solar radiation, or radiogenic decay [6]. These samples all have low H contents, C/H (bulk), and low 17O [6,8] and may hold clues to understanding the mineralogy of Ryugu, or interpretations of its spectral properties. WIS 91600, on the other hand, appears to be related to several other highly altered CM [6], and shares properties with the newly proposed CY chondrites [6]. An understanding of this grouplet will also aid in the interpretation of Bennu samples which have strong hydration features. In addition, ungrouped carbonaceous chondrites may provide valuable insights into the aqueous alteration potentially recorded in Bennu and Ryugu samples; such as the relatively moderate aqueous alteration recognized and dated at 4-5 myr after CAIs in MAC 88107 (C2-ungrouped) by [9] to the extensive aqueous alteration apparent in MIL 090292 (C1-ungrouped) [10]. Finally, LON 94101/94102 is a brecciated CM chondrite with numerous lithologies. Its appearance is similar to some of the brecciated lithologies visible at the surface of Bennu and Ryugu [11]. Although CM chondrites with multiple lithologies are common (e.g., [12]), the lithologies are often difficult to resolve at the hand specimen scale and only after some detailed e-beam characterization are the subtle lithologic differences evident (e.g., [13]). LON 94102 contains visibly distinct clasts at the hand specimen scale, relatively rare for CM breccias. The largest CM chondrites by mass from the U.S. Antarctic meteorite collection may provide insights into the extent of brecciation and heterogeneity within more typical CM chondrite-like source asteroids. For example, recent curation CT scans [14] show possible clasts within in a subsplit of ALH 83100 (CM1/2) which is the largest CM chondrite or CM chondrite pairing group in the U.S. Antarctic collection with an original mass of 3.019 kg. Similar work on additional subsplits or meteorites may aid our understanding of heterogeneity within CM chondrites from Antarctica. Initial classification of CM chondrites in U.S. Antarctic meteorite collection includes preliminary pairing when petrographically similar CM chondrites that have been previously found in the same field area. The two largest CM chondrite preliminary pairing groups by mass are the ALH 83102 (CM2) pairing group with an original mass of 2.554 kg and the EET 96005 (CM2) pairing group with an original mass of 1.125 kg. However, preliminary pairing groups assigned at classification—intrinsically— do not include stones that are petrographically distinct. Rigorous pairing group studies of CM chondrites from specific field sites are needed to investigate if there is unrecognized heterogeneity in CM chondrites from Antarctica that may represent common asteroid impactors (pre-atmospheric entry asteroids/meteoroids). Detailed pairing studies have the potential to recognize initial stones with multiple lithologies and investigate if there are stones that only sample one of those respective lithologies in the collection. These groups of heated CMs, extensively hydrated CMs, intermediate between CM and CO chondrites, and brecciated samples are all potentially relevant to Bennu and Ryugu samples, where heating, hydration, and brecciation have all come into play. These bodies might also be comprised of material intermediate to CM and CO chondrites, or at least distinct from the well-established CC groups. These small and unusual groups of carbonaceous chondrites may help to unlock new information about early solar system processes and aid in the understanding of the evolution of these carbonaceous asteroids.

meteorites↗

Anisotropy and shear-velocity heterogeneities in the upper mantle

Long-period surface waves are used to map lateral heterogeneities of velocity and anisotropy in the upper mantle. The dispersion curves are expanded in spherical harmonics up to degree 6 and inverted to find the depth structure. The data are corrected for the effect of surface layers and both Love and Rayleigh waves are used. Shear wave velocity and shear polarization anisotropy can be resolved down to a depth of about 450 km. The shear wave velocity distribution to 200 km depth correlates with surface tectonics, except in a few anomalous regions. Below that depth the correlation vanishes. Cold subducted material shows up weakly at 350 km as fast S-wave anomalies. In the transition region a large scale pattern appears with fast mantle in the South-Atlantic. S-anisotropy at 200 km can resolve uprising or downwelling currents under some ridges and subduction zones. The Pacific shows a NW-SE fabric.

Nataf, H.-C.↗

Analysis of Plasma-Sprayed Thermal Barrier Coatings With Homogeneous and Heterogeneous Bond Coats Under Spatially Uniform Cyclic Thermal Loading

This report summarizes the results of a numerical investigation into the spallation mechanism in plasma-sprayed thermal barrier coatings observed under spatially-uniform cyclic thermal loading. The analysis focuses on the evolution of local stress and inelastic strain fields in the vicinity of the rough top/bond coat interface during thermal cycling, and how these fields are influenced by the presence of an oxide film and spatially uniform and graded distributions of alumina particles in the metallic bond coat aimed at reducing the top/bond coat thermal expansion mismatch. The impact of these factors on the potential growth of a local horizontal delamination at the rough interface's crest is included. The analysis is conducted using the Higher-Order Theory for Functionally Graded Materials with creep/relaxation constituent modeling capabilities. For two-phase bond coat microstructures, both the actual and homogenized properties are employed in the analysis. The results reveal the important contributions of both the normal and shear stress components to the delamination growth potential in the presence of an oxide film, and suggest mixed-mode crack propagation. The use of bond coats with uniform or graded microstructures is shown to increase the potential for delamination growth by increasing the magnitude of the crack-tip shear stress component.

Arnold, Steven M.↗

Vesta and the HED Meteorites: Comparison of Spectral Properties

We present the main results obtained comparing the visible-near infrared (VIS-NIR) spectra Vesta s surface with howardites, eucrites, diogenites (HEDs). HEDs are commonly associated with Vesta based on spectral similarities. Because of such association, much effort is being made to merge the information from HEDs as well as Vestoids with that from Vesta to characterize the lithologic diversity of the surface of this asteroid and to infer clues regarding its thermal history. The Dawn spacecraft, orbiting around Vesta since July 2011, is performing detailed observations of this body and thus improving our knowledge of its properties. Dawn s scientific payload includes an imaging spectrometer, VIR-MS, sensitive to the VIS-NIR spectral range. VIR-MS began acquiring spectra during the approach phase that started in May 2011 and will continue its observations through July 2012 when the spacecraft will depart Vesta to travel to Ceres. The observations are uniformly distributed in latitude and longitude, allowing a global view of Vesta s crustal spectral properties. Using the information provided by VIR spectra, we studied the distribution of the spectral heterogeneities on the surface and used our findings to perform a comparison with HED spectra in the VIS-NIR spectral range searching for analogies and/or incompatibilities. In our analysis, we utilized a method to compare the results obtained at microscopic scale on HED samples and the one obtained at macroscopic scale on the surface of Vesta. The intent of this study is to improve our understanding of the connection between Vesta and the HEDs, which is one of the primary Dawn scientific objectives. Dawn VIR spectra are characterized by pyroxene absorptions and most of the surface materials exhibit howardite-like spectra. However, some large areas can be interpreted to be material richer in diogenite (based on pyroxenes band depths and band centers) and some others like eucrite-rich howardite terrains. In particular, VIR data strongly indicate in the south polar region (Rheasilvia) the presence of Mg-pyroxene-rich terrains. The hypothesis that Vesta is the HED parent body is consistent with, and strengthened by, the geologic and spectral context for pyroxene distribution provided by VIR on Dawn.

Ammannito, E.↗

Atmospheric Chemistry of Micrometeoritic Organic Compounds

Micrometeorites approx.100 m in diameter deliver most of the Earth s annual accumulation of extraterrestrial material. These small particles are so strongly heated upon atmospheric entry that most of their volatile content is vaporized. Here we present preliminary results from two sets of experiments to investigate the fate of the organic fraction of micrometeorites. In the first set of experiments, 300 m particles of a CM carbonaceous chondrite were subject to flash pyrolysis, simulating atmospheric entry. In addition to CO and CO2, many organic compounds were released, including functionalized benzenes, hydrocarbons, and small polycyclic aromatic hydrocarbons. In the second set of experiments, we subjected two of these compounds to conditions that simulate the heterogeneous chemistry of Earth s upper atmosphere. We find evidence that meteor-derived compounds can follow reaction pathways leading to the formation of more complex organic compounds.

Kress, M. E.↗

A Partitioned -Task Parallel Implementation of the NASA Multiscale Analysis Tool for High Performance Computing

The NASA Multiscale Analysis Tool (NASMAT) is a “plug and play” software package that allows users to conduct massively multiscale modeling of hierarchical and nonlinear materials. This work extends the scalability and improves the High Performance Computing friendliness of NASMAT by adopting a Partitioned Task-Parallel approach. Interoperability of NASMAT with external software is enhanced through preCICE, a open source library for multiphysics coupling in a partitioned manner. Enhancement through preCICE allows for easy integration of NASMAT to other macro solvers and dissociates the parallelization strategy adopted within NASMAT from the macro solver. The task-parallel framework based on Master-Worker approach is implemented as the parallelization scheme. The scheme accounts for hierarchy of multiple scales (task-dependence) and heterogeneous nature (dynamic load balancing) of computations. The applicability and scalability of the framework will be evaluated by analyzing large scale engineering problems through massively multiscale methods.

NASMAT↗

Chondrites and the Protoplanetary Disk, Part 1

The papers discussed the following: The Formation Process of Adhering and Consorting Compound Chondrules Inferred Their Petrology and Major-Element Composition. The Prospect of High-Precision Pb Isotopic Dating of Meteorites. Evolution of UV-Irradiated Protoplanetary Disks. A Model for the Formation of E Chondrites. Oxygen Isotopic Diffusion and Exchange Experiments on Olivine and Chondrule Melts: Preliminary Results. Shock Heating: Origin of Shock Waves in the Protoplanetary Disk. Thermal Structures of Protoplanetary Disks. Meteoritical Astrophysics: A New Subdiscipline. Origin and Thermal History of FeNi-Metal in Primitive Chondrites. The Collisions of Chondrules Behind Shock Waves. Primary Signatures of the Nebular Dust Preserved in Accretionary Rims and Matrices of CV Chondrites. History of Thermally Processed Solids in the Protoplanetary Disk: Reconciling Theoretical Models and Meteoritical. Evidence Evaporation and Condensation During CAI and Chondrule Formation. Shock Heating: Effects on Chondritic Material. Rhounite-bearing Inclusions E201 and E202 from Efremovka: Constraints from Trace. Element Measurements Element Mapping in Anhydrous IDPs: Identification of the Host Phases of Major/Minor Elements as a Test of Nebula Condensation Models. Theoretical Studies of Disk Evolution Around Solar Mass Stars. Chemical Effects of High-Temperature Processing of Silicates. I-Xe and the Chronology of the Early Solar System. The Effects of X-Rays on the Gas and Dust in Young Stellar Objects. Origin of Short-lived Radionuclides in the Early Solar System. On Early Solar System Chronology: Implications of an Initially Heterogeneous Distribution of Short-lived Radionuclides. The Origin of Short-lived Radionuclides and Early Solar System Irradiation. Disequilibrium Melting and Oxygen Isotope Exchange of CAIs and Chondrules in the Solar Nebula. Mineralogy and Chemistry of Fine-grained Matrices, Rims, and Dark Inclusions in the CR Carbonaceous Chondrites Acfer/El Djouf 001 and the Ungrouped Carbonaceous Chondrites Acfer 094 and Adelaide. Oxygen Isotopes of Aluminum-rich Chondrules from Unequilibrated Enstatite Chondrites.

Source record↗

Basalt generation at the Apollo 12 site. Part 2: Source heterogeneity, multiple melts, and crustal contamination

The petrogenesis of Apollo 12 mare basalts has been examined with emphasis on trace-element ratios and abundances. Vitrophyric basalts were used as parental compositions for the modeling, and proportions of fractionating phases were determined using the MAGFOX prograqm of Longhi (1991). Crystal fractionation processes within crustal and sub-crustal magma chambers are evaluated as a function of pressure. Knowledge of the fractionating phases allows trace-element variations to be considered as either source related or as a product of post-magma-generation processes. For the ilmenite and olivine basalts, trace-element variations are inherited from the source, but the pigeonite basalt data have been interpreted with open-system evolution processes through crustal assimilation. Three groups of basalts have been examined: (1) Pigeonite basalts-produced by the assimilation of lunar crustal material by a parental melt (up to 3% assimilation and 10% crystal fractionation, with an 'r' value of 0.3). (2) Ilmenite basalts-produced by variable degrees of partial melting (4-8%) of a source of olivine, pigeonite, augite, and plagioclase, brought together by overturn of the Lunar Magma Ocean (LMO) cumulate pile. After generation, which did not exhaust any of the minerals in the source, these melts experienced closed-system crystal fractionation/accumulation. (3) Olivine basalts-produced by variable degrees of partial melting (5-10%) of a source of olivine, pigeonite, and augite. After generation, again without exhausting any of the minerals in the source, these melts evolved through crystal accumulation. The evolved liquid counterparts of these cumulates have not been sampled. The source compositions for the ilmenite and olivine basalts were calculated by assuming that the vitrophyric compositions were primary and the magmas were produced by non-modal batch melting. Although the magnitude is unclear, evaluation of these source regions indicates that both be composed of early- and late-stage Lunar Magma Ocean (LMO) cumulates, requiring an overturn of the cumulate pile.

Neal, Clive R.↗

Structural Weight Estimation for Launch Vehicles

This paper describes some of the work in progress to develop automated structural weight estimation procedures within the Vehicle Analysis Branch (VAB) of the NASA Langley Research Center. One task of the VAB is to perform system studies at the conceptual and early preliminary design stages on launch vehicles and in-space transportation systems. Some examples of these studies for Earth to Orbit (ETO) systems are the Future Space Transportation System [1], Orbit On Demand Vehicle [2], Venture Star [3], and the Personnel Rescue Vehicle[4]. Structural weight calculation for launch vehicle studies can exist on several levels of fidelity. Typically historically based weight equations are used in a vehicle sizing program. Many of the studies in the vehicle analysis branch have been enhanced in terms of structural weight fraction prediction by utilizing some level of off-line structural analysis to incorporate material property, load intensity, and configuration effects which may not be captured by the historical weight equations. Modification of Mass Estimating Relationships (MER's) to assess design and technology impacts on vehicle performance are necessary to prioritize design and technology development decisions. Modern CAD/CAE software, ever increasing computational power and platform independent computer programming languages such as JAVA provide new means to create greater depth of analysis tools which can be included into the conceptual design phase of launch vehicle development. Commercial framework computing environments provide easy to program techniques which coordinate and implement the flow of data in a distributed heterogeneous computing environment. It is the intent of this paper to present a process in development at NASA LaRC for enhanced structural weight estimation using this state of the art computational power.

Cerro, Jeff↗

Tough composite materials: Recent developments

The present volume broadly considers topics in composite fracture toughness and impact behavior characterization, composite system constituent properties and their interrelationships, and matrix systems' synthesis and characterization. Attention is given to the characterization of interlaminar crack growth in composites by means of the double cantilever beam specimen, the characterization of delamination resistance in toughened resin composites, the effect of impact damage and open holes on the compressive strength of tough resin/high strain fiber laminates, the effect of matrix and fiber properties on compression failure mechanisms and impact resistance, the relation of toughened neat resin properties to advanced composite mechanical properties, and constituent and composite properties' relationships in thermosetting matrices. Also treated are the effect of cross-link density on the toughening mechanism of elastomer-modified epoxies, the chemistry of fiber/resin interfaces, novel carbon fibers and their properties, the development of a heterogeneous laminating resin, solvent-resistant thermoplastics, NASA Lewis research in advanced composites, and opportunities for the application of composites in commercial aircraft transport structures.

Vosteen, L. F.↗

Fission track astrology of three Apollo 14 gas-rich breccias

The three Apollo 14 breccias 14301, 14313, and 14318 all show fission xenon due to the decay of Pu-244. To investigate possible in situ production of the fission gas, an analysis was made of the U-distribution in these three breccias. The major amount of the U lies in glass clasts and in matrix material and no more than 25% occurs in distinct high-U minerals. The U-distribution of each breccia is discussed in detail. Whitlockite grains in breccias 14301 and 14318 found with the U-mapping were etched and analyzed for fission tracks. The excess track densities are much smaller than indicated by the Xe-excess. Because of a preirradiation history documented by very high track densities in feldspar grains, however, it is impossible to attribute the excess tracks to the decay of Pu-244. A modified track method has been developed for measuring average U-concentrations in samples containing a heterogeneous distribution of U in the form of small high-U minerals. The method is briefly discussed, and results for the rocks 14301, 14313, 14318, 68815, 15595, and the soil 64421 are given.

Graf, H.↗

Heterogeneity Determination and Purification of Commercial Hen Egg-White Lysozyme

Hen egg-white lysozyme (HEWL) is widely used as a model protein, although its purity has not been adequately characterized by modern biochemical techniques. We have identified and quantified the protein heterogeneities in three commercial HEWL preparations by sodium dodecyl sulfate polyacrylamide gel electrophoresis with enhanced silver staining, reversed-phase fast protein liquid chromatography (FPLC) and immunoblotting with comparison to authentic protein standards. Depending on the source, the contaminating proteins totalled 1-6%(w/w) and consisted of ovotransferrin, ovalbumin, HEWL dimers, and polypeptides with approximate M(sub r) of 39 and 18 kDa. Furthermore, we have obtained gram quantities of electrophoretically homogeneous [> 99.9%(w/w)] HEWL by single-step semi-preparative scale cation-exchange FPLC with a yield of about 50%. Parallel studies of crystal growth kinetics, salt repartitioning and crystal perfection with this highly purified material showed fourfold increases in the growth-step velocities and significant enhancement in the structural homogeneity of HEWL crystals.

Thomas, B. R.↗

Nanostructure and compositional segregation of soft magnetic FeNi-based nanocomposites with multiple nanocrystalline phases

Soft magnetic metal amorphous nanocomposite alloys are produced through rapid solidification and thermal annealing yielding nanocrystals embedded within an amorphous precursor. Similar free energies in Co-rich and FeNi-based alloy systems result in multiple nanocrystalline phases being formed during devitrification. Studies of multi-phase crystallization processes have been reported for Co-rich alloys but relatively few have investigated FeNi-based systems. A detailed characterization of compositional partitioning and microstructure of an optimally annealed FeNi-based MANC (Fe70Ni30)80Nb4Si2B14 alloy is presented through complementary high-resolution transmission electron microscopy (HRTEM) and atom probe tomography (APT). HRTEM demonstrates orientation relationships between FCC and BCC nanocrystals, suggesting heterogeneous nucleation of nanocrystals in the amorphous matrix or a cooperative mechanism of nucleation between BCC and FCC nanocrystallites. APT results show evidence for (i) the segregation of Fe and Ni between nanocrystals of different phases, (ii) B partitioning to the amorphous phase, and (iii) an Nb-enriched shell surrounding nanocrystals.

soft magnetic materials↗

A Partitioned - Task Parallel Implementation of the NASA Multiscale Analysis Tool for High Performance Computing

The NASA Multiscale Analysis Tool (NASMAT) is a platform for multiscale modeling of composites which can perform analysis of materials with any arbitrary number of length scales. The platform supports modularity, scalability, and interoperability using recursive procedures and data structures. A Macro solver driven parallelization scheme often limits the capability of NASMAT to scale as it has access to limited memory and number of cores (often one core/thread) and often forces to implement macro solver specific changes to the platform. In this work, a partitioned task-parallel approach is adopted, where the parallelization strategy adopted for NASMAT is independent of the macro solver and the computational resources are managed independently. The programming architecture takes into account the hierarchy of multiple scales (task-dependence) and the heterogeneous nature (dynamic load balancing) of computation through implementation of a hierarchy-informed task parallel model. The partitioned nature of the framework further extends the “plug and play” capability of NASMAT. preCICE, an open-source library for coupling multiphysics solver in a partitioned manner, is adopted to integrate NASMAT with an external macro solver by implementing a NASMAT adapter for preCICE. Speedup and scalability of the framework is studied for micromechanical models of varying size.

task-parallel↗

Evidence for a Single Ureilite Parent Asteroid from a Petrologic Study of Polymict Ureilites

Ureilites are ultramafic achondrites composed of olivine and pyroxene, with minor elemental C, mostly as graphite [1]. The silicate composition indicates loss of a basaltic component through igneous processing, yet the suite is very heterogeneous in O isotopic composition inherited from nebular processes [2]. Because of this, it has not yet been established whether ureilites were derived from a single parent asteroid or from multiple parents. Most researchers tacitly assume a single parent asteroid, but the wide variation in mineral and oxygen isotope compositions could be readily explained by an origin in multiple parent asteroids that had experienced a similar evolution. Numerous ureilite meteorites have been found in Antarctica, among them several that are clearly paired (Fig. 1) and two that are strongly brecciated (EET 83309, EET 87720). We have begun a detailed petrologic study of these latter two samples in order to characterize the range of materials in them. One goal is to attempt to determine whether ureilites were derived from a single parent asteroid.

Downes, Hilary↗

A Transmission Electron Microscopy Study of a Refractory Metal Grain from a Calcium-Aluminum-Rich Inclusion in the Leoville CV3 Chondrite

Introduction: Calcium-aluminum-rich inclusions (CAIs) are an important component of chondritic meteorites. They can contain materials that are thermodynamically predicted and isotopically age dated to be among the first-formed solids in our solar system [1-5]. Observed in some CAIs are micron to sub-micron sized inclusions rich in Fe, Ni, and high-Z elements such as Pt, Os, Ir and W, in the form of refractory metal nuggets (RMNs), fremdlinges, and ‘nugget like objects’ (NLOs) [1,6]. Refractory siderophile elements such as Os, Ir and Ru are thermodynamically predicted to condense at temperatures well in excess of the major CAI phases such as melilite, perovskite, spinel and hibonite [2,7-9]. These refractory metal inclusions in CAIs can therefore serve as probes into the thermodynamic landscape of the early solar protoplanetary disk. Here we report on a refractory grain identified in a CAI of the Leoville CV3 chondrite. This work is part of an ongoing effort to gain insight into the thermochemistry of the early solar system through systematic analyses of the structure and chemistry of various components in CAIs [10-13]. Sample and Analytical Techniques: A fluffy type A CAI (Fig. 1A) was identified in a section of the Leoville, CV3 chondrite (Center for Meteorite Studies, Arizona State University collection, #821_C_3) using a JOEL-JXA 8530F electron microprobe at Arizona State University. Backscattered electron (BSE) imaging and energy-dispersive X-ray spectroscopy (EDS) were used to identify refractory metal grains in the CAI using a Thermo Fisher (formerly FEI) Helios NanoLab 660 G3 focused-ion-beam scanning-electron microscope (FIBSEM) located at the Kuiper Materials Imaging and Characterization Facility (KMICF) at the Lunar and Planetary Laboratory, University of Arizona. The FIB is equipped with an EDAX EDS system. We selected one of the larger (micron-sized) refractory metal grains, designated as ‘Spud’ (Fig. 1B) for further analysis. ‘Spud’ was extracted and thinned to electron transparency (<100 nm) using the FIB-SEM located in KMICF, following methods described by [14- 15]. The FIB section was analyzed using a 200 keV Hitachi HF5000 scanning transmission electron microscope (S/TEM) located at KMICF. The HF5000 is equipped with cold-field emission gun, 3rd-order spherical aberration corrector for STEM imaging, and an Oxford Instruments X-Max N 100 TLE energydispersive spectroscopy (EDS) system with dual 100 mm2 windowless silicon-drift detectors (Ω = 2.0 sr). Selected-area electron-diffraction (SAED) patterns were acquired to aid in determination of crystallinity and phase. Results: The mineralogy, texture, and morphology of the CAI are consistent with that of a fluffy type A (FTA) CAI [16]. BSE imaging at high magnifications revealed grains with high contrast, indicative of compositions rich in elements of higher atomic number relative to surrounding material. These high-Z grains have sizes that range from ∼250 nm to 4 µm. EDS analyses confirm that the bright grains are metal-rich inclusions. A minor fraction of the grains are composed of only Fe and Ni, but the majority (∼60%) of the identified inclusions also contained various refractory siderophiles including Os, Ru, Zr, Ir and Mo. EDS analysis on the FIB-SEM of Spud shows that it contains Fe, Ni, Mo and Ru. High-angle annular dark-field (HAAFD) imaging and EDS mapping in the TEM (Fig. 2) show that Spud occurs in melilite (Ca1.9Al1.99Si1.06O7). Spud contains a subhedral to anhedral morphology and is compositionally heterogenous (polyphasic, Fig. 2). Local spatial correlation occurs among Fe, Ni, and Pt, and also among Os, Ru, and Mo. SAED patterns show that the Fe-Ni-Pt, Fe-Os-Mo-Ru and Fe-Pt regions are crystalline. Discussion: CAIs can contain various types of inclusions rich in Fe, Ni and refractory siderophiles such as Os, Ru, W and Pt [1]. RMNs are micron-sized, single phase alloy grains and can contain Os, Ir, Ru and Rh [1,7,17]. NLOs are also micron-sized inclusions, but contain two phases, a refractory metal, and an oxide [6]. Fremdlinge are the largest of such inclusions (tens of microns in size) and are complex aggregates of Fe-Ni alloy, silicates, oxides, and sulfides [1,17]. While the size of Spud matches previous descriptions of RMNs and NLOs, Spud is neither a single-phase alloy like RMNs, nor does it contain one metal phase and one oxide like NLOs. Spud does not match the above described categories of refractory metal inclusions. The presence of refractory siderophiles such as Mo, Os, Ru, and Pt suggests a high-temperature origin. Thermodynamic modelling by [7] indicates condensation temperatures of 1917 K, 1693 K, 1613 K and 1415 K for Os, Mo, Ru and Pt respectively. These models also show that following the initial condensation of a refractory metal, alloying of solutes such as Fe, Ni and W, occurs in levels proportional to their partial pressures in the surrounding gas. Such alloying occurs at temperatures above the condensation temperatures of common CAI phases such as melilite (1529 K), perovskite (1441 K), spinel (197 K) and forsterite (1354 K) [2]. The polyphasic nature of Spud could be the result of such high-temperature alloying, possibly shortly after the condensation of Mo and Ru at 1693 K and 1613 K respectively. That Spud occurs as an inclusion is consistent with it having formed prior to and at temperature above that of its host melilite in this FTA CAI, which is qualitatively consistent with such prior thermodynamic modeling. Further, the polyphasic nature of Spud is similar to refractory grains from a FTA CAI in the Northwest Africa (NWA) 8323, CV3 chondrite [11-13]. These data suggest that such refractory metal grains could have been widespread in the inner and early solar protoplanetary disk and represent some of the earliest formed solids to have condensed. Acknowledgments: Research and instrumentation supported by NASA grants #NNX12AL47G, #NNX15AJ22G and #80NSSC19K0509, and NSF grants #1531243 and #0619599. Fig 2. STEM data on ‘Spud’. HAADF Image (Top) False-color EDS Maps (Bottom) References: [1] MacPherson G. J. (2014) T. of Geochem. Vol I: Met. And Cosmochem. Processes, 139-179. [2] Lodders K. (2003) ApJ, 591, 1220-1247. [3] Ebel D. S. (2006) Met. & the Early S. Sys. II., 253- 277. [4] Amelin Y. (2002) Science, 297, 1678-1683. [5] Connelly J.N. et.al. (2012) Science, 338, 651-655. [6] Schwander D. et al. (2015) GCA, 18, 70-87. [7] Palme H. and Wlotzka F. (1976) EPSL, 33, 45-60. [8] Berg T. et al. (2009) ApJ, 702, 172-176. [9] Liffman K. et al. (2021) Icarus, 221, 89-105. [10] Zega T.J. et al. (2021) PSJ, 2, 115. [11] Ramprasad T. et al. (2020) LPSC LI, Abstract #2472. [12] Ramprasad T. et al. (2021) Microscopy & Microanalysis, S1, 2792-2794. [13] Ramprasad T. et al. (2021) 84th MetSoc, Abstract #6123. [14] Zega T.J. et al. (2007) MAPS, 42, 1373-1386. [15] Ramprasad T. et al. (2022) MAPS, in revision. [16] Grossman L. (1975), GCA, 39, 433-454. [17] El Goresy A. et al. (1978) LPSC IX, Abstract#1100

T. Ramprasad↗

Chronology of chrondrule and CAI formation: Mg-Al isotopic evidence

Details of the chondrule and Ca-Al-rich inclusion (CAI) formation during the earliest history of the solar system are imperfectly known. Because CAI's are more 'refractory' than ferromagnesian chondrules and have the lowest recorded initial Sr-87/Sr-86 ratios of any solar system materials, the expectation is that CAI's formed earlier than chondrules. But it is not known, for example, if CAI formation had stopped by the time chondrule formation began. Conventional (absolute) age-dating techniques cannot adequately resolve small age differences (less than 10(exp 6) years) between objects of such antiquity. One approach has been to look at systematic differences in the daughter products of short-lived radionuclides such as Al-26 and I-129. Unfortunately, neither system appears to be 'well-behaved.' One possible reason for this circumstance is that later secondary events have partially reset the isotopic systems, but a viable alternative continues to be large-scale (nebular) heterogeneity in initial isotopic abundances, which would of course render the systems nearly useless as chronometers. In the past two years the nature of this problem has been redefined somewhat. Examination of the Al-Mg isotopic database for all CAI's suggests that the vast majority of inclusions originally had the same initial Al-26/Al-27 abundance ratio, and that the ill-behaved isotopic systematics now observed are the results of later partial reequilibration due to thermal processing. Isotopic heterogeneities did exist in the nebula, as demonstrated by the existence of so-called FUN inclusions in CV3 chondrites and isotopically anomalous hibonite grains in CM2 chondrites, which had little or no live Al-26 at the time of their formation. But, among the population of CV3 inclusions at least, FUN inclusions appear to have been a relatively minor nebular component.

Macpherson, G. J.↗