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At least 577 records · Page 32

More on the Possible Composition of the Meridiani Hematite-Rich Concretions

Elsewhere in these proceedings, Schneider et al. discuss compositional constraints on hematite-rich spherule (blueberry) formation at Meridiani Planum. Schneider et al. provide the background for work done to date to understand the composition and mineralogy of the spherules and devise a test of possible concretion growth processes. They also report the results of area analyses of spherules in targets analyzed with the Alpha Particle X-ray Spectrometer (APXS) and test several possible models for included components other than hematite. In this abstract, we use the compositional trends for spherule-rich targets to compute possible elemental compositions of the spherules. This approach differs from that of, which also used a determination of the area of spherules in APXS targets, coupled with a correction for the radial acceptance function, to try to un-mix the compositions directly, using 2 and 3-component models and mass balance. That approach contained a fair amount of uncertainty owing to problems associated with irregular and heterogeneous target geometry, unknown composition of non-spherule lithic components, and variable dust coatings on spherules. Since then, Opportunity has analyzed additional spherule-rich targets, and the compositional trends so obtained permit a more direct assessment of the data.

Jolliff, B. L.↗

The Role of CO2 in Aqueous Alteration of Ultra-Mafic Rocks and the Formation of MF-,FE-Rich Aqueous Solutons on Early Mars

An adequate understanding of water on Mars that moves beyond the simplistic "warmwet" vs. "cold-dry" dichotomy must include strong constraints on the variables: water/rock ratio, time, temperature, and chemical composition. By constraining these variables first on local, then regional and global scales we will be capable of precisely targeting landed missions to definitively understand the history of water on Mars and the possible existence of life. Data from remote sensing of Mars, landed missions, and martian meteorites indicate that secondary minerals formed from aqueous fluids on Mars are predominately Fe- and Mg-rich. The unique Mg-, Fe-rich carbonates in the ALH 84001 meteorite provide an excellent opportunity to provide strong constraints on an Fe-, Mg-rich aqueous system on early Mars. This work seeks to use the unusual chemical compositions of the ALH 84001 carbonates as a constraint for the composition of their formation fluid. These constraints can be used to better understand aqueous processes at a critical time in martian history.

Niles, Paul B.↗

Characterizing of a Mid-Latitude Ice-Rich Landing Site on Mars to Enable in Situ Habitability Studies

We suggest an ice-rich landing site at 188.5E 46.16N within Amazonis Planitia as a candidate location to support a Mars lander mission equipped to study past habitability and regions capable of preserving the physical and chemical signs of life and organic matter. Studies of the ice-rich subsurface on Mars are critical for several reasons. The subsurface environment provides protection from radiation to shield organic and biologic compounds from destruction. The ice-rich substrate is also ideal for preserving organic and biologic molecules and provides a source of H2O for biologic activity. Examination of martian ground ice can test several hypotheses such as: 1) whether ground ice supports habitable conditions, 2) that ground ice can preserve and accumulate organic compounds, and 3) that ice contains biomolecules evident of past or present biological activity on Mars. This Amazonis site, located near the successful Viking Lander 2, shows indirect evidence of subsurface ice (ubiquitous defined polygonal ground, gamma ray spectrometer hydrogen signature, and numerical modeling of ice stability) and direct evidence of exposed subsurface ice. This site also provides surface conditions favorable to a safe landing including no boulders, low rock density, minimal rough topography, and few craters.

Heldmann, J.↗

Rb-Sr Isotopic Systematics of Alkali-Rich Fragments in the Yamato-74442 LL-Chondritic Breccia

Alkali-rich igneous fragments were identified in the brecciated LL-chondrites, Kr henberg (LL5)], Bhola (LL3-6) and Yamato (Y)-74442 (LL4), and show characteristic fractionation patterns of alkaline elements. The K-Rb-Cs-rich fragments in Kr henberg, Bhola, and Y-74442 are very similar in mineralogy and petrography (olivine + pyroxene + glass), suggesting that they could have come from related precursor materials. We have undertaken Rb-Sr isotopic studies on alkali-rich fragments in Y-74442 to precisely determine their crystallization ages and the isotopic signatures of their precursor material(s).

Yokoyama, T.↗

Evidence of Metasomatism in the Lowest Petrographic Types Inferred from A Na(-), K, Rich Rim Around A LEW 86018 (L3.1) Chondrule

Ordinary chondrites (OCs) represent the most abundant extraterrestrial materials and also record the widest range of alteration of primary, pristine minerals of early Solar system material available for study. Relatively few investigations, however, address: (1) the role of fluid alteration, and (2) the relationship between thermal metamorphism and metasomatism in OCs, issues that have been extensively studied in many other meteorite groups e.g., CV, CO, CR, and enstatite chondrites. Detailed elemental abundances profiles across individual chondrules, and mineralogical studies of Lewis Hills (LEW) 86018 (L3.1), an unequilibrated ordinary chondrite (UOC) of low petrographic type of 3.1 returned from Antarctica, provide evidence of extensive alteration of primary minerals. Some chondrules have Na(-), K(-), rich rims surrounded by nepheline, albite, and sodalite-like Na(-), Cl(-), Al-rich secondary minerals in the near vicinity within the matrices. Although, limited evidences of low temperature (approximately 250 C) fluid-assisted alteration of primary minerals to phyllosilicates, ferroanolivine, magnetite, and scapolite have been reported in the lowest grades (less than 3.2) Semarkona (LL3.00) and Bishunpur (LL3.10), alkali-rich secondary mineralization has previously only been seen in higher grade greater than 3.4 UOCs. This preliminary result suggests highly localized metamorphism in UOCs and widens the range of alteration in UOCs and complicates classification of petrographic type and extent of thermal metamorphism or metasomatism. The work in progress will document the micro-textures, geochemistry (Ba, Ca, REE), and isotopic composition (oxygen, Al(-)- 26 Mg-26) of mineral phases in chondrules and adjoining objects to help us understand the formation scenario and delineate possible modes of metamorphism in UOCs.

Mishra, Ritesh Kumar↗

Microstructural Record of Evolving Condensation Processes in Fine-Grained Ca-Al-Rich Inclusions from the Reduced CV3 Chondrites

Fine-grained, spinel-rich Ca-Al-rich inclusions (FGIs) in carbonaceous chondrites consist of numerous layered nodules having cores of spinel, hibonite, and/or perovskite surrounded by multiple thin layers of melilite, anorthite, diopside, and/or olivine. They are interpreted as aggregates of direct high-temperature condensates from an 16O-rich nebular gas that escaped significant melting. However, FGIs are very complex objects composed of intimate intergrowths of fine-grained refractory phases and show extremely large variations in mineralogy, modal abundance, and textures. Thus, detailed FIB/TEM analyses of FGIs are required to fully characterize their micro-to-nanometer scale textures, mineralogy, and chemical compositions and hence elucidate their formation processes and conditions in the early solar nebula. Here, we present our on-going study of pristine FGIs from the reduced CV3 chondrites Efremovka and Thiel Mountains (TIL) 07003 and 07007 that have minimal evidence for secondary parent body alteration.

Han, J.↗

Recent Developments in the Curation of Cold, Volatile-Rich Extraterrestrial Samples

In recent years, the study of samples from cold, potentially volatile-rich Solar System bodies has increased dramatically. Returned samples from low- or cryogenic-temperature regions are highly sensitive to ambient temperatures, pressures, and materials. In order to maximize the scientific utility of such samples, they must be returned, handled, and stored under conditions that minimize sample alteration and contamination. The Johnson Space Center (JSC) Astromaterials Acquisition and Curation Office (hereafter called the Curation Office) is currently developing the ability to curate cold, volatile-rich samples; this abstract summarizes these efforts for Apollo lunar samples, organic-rich meteorites, comet samples, and lunar polar samples.

Mitchell, J. L.↗

Compositional Clues to the Origin of Refractory Metal Nuggets, Perovskite, and Zr-Rich Oxides in Hibonite from the Paris Cm Chondrite

Rare Ca-Al-rich inclusions (CAIs) in carbonaceous chondrites are dominated by Zr-, Sc-, Ti-,and/or Y-rich oxides and silicates, and often contain refractory metal nuggets (RMNs)[1-3]. These phases have ultra refractory (UR) rare earth element (REE)patterns that are complementary to Group II patterns[4]. Therefore, studies of such UR CAIs likely decipher a record of nebular conditions and processes at higher temperatures than other CAIs consisting mainly of spinel and melilite. Our previous TEM analyses reported a discovery of the assemblages of RMNs, perovskite, and Zr-rich oxides in hibonite from the Paris CM chondrite[5]. Here we present TEM results of a detailed chemical study of these UR phases to provide clues to their formation conditions in the early solar nebula.

J Han↗

Terrestrial Aqueously Altered Magmatic Dike Forming Sulfate-Rich Hydrothermal Fluids to Constrain Martian Habitability

Intrusion of magma into a water-bearing crust can create a habitable hydrothermal environment, as seen on Earth. As the rock surrounding the intrusion is subjected to heat it can 1) release water, and different chemical species, from pre-existing minerals, and 2) interact with volatiles released from the cooling magma, which can create a geothermal brine with a distinct composition suitable for a range of chemotrophs. Hence, studying such environments on Earth is important in the search for life beyond our planet. The geothermal brine’s nature is dependent on the host rock and the magmatic properties. On Mars basaltic and sulfur-rich soils are dominant and therefore investigating basaltic magmatic interaction with sulfate-rich sediments and their associated habitats is key for recognizing potential habitats on Mars. The NASA Perseverance Rover at Jezero Crater has detected aqueously altered igneous rocks, potentially intrusive in origin, with secondary carbonates, sodium perchlorate and sulfates. Such an environment may have been habitable. Therefore, we investigate the intrusion of a magmatic dike into Jurassic sulfate-rich sediments from the San Rafael Swell, Utah, to reconstruct the geothermal fluids and assess their putative habitability.

B Baharier↗

The Chemical and Isotopic Signatures of the Hibonite-rich FUN Inclusion "HIDALGO" in Dar al Gani 027 (CO3)

Refractory Ca-Al-rich Inclusions (CAIs) with FUN (Fractionation with Unidentified Nuclear effects) characteristics are peculiar samples among all high-temperature components in chondritic meteorites. They are generally characterized by strong mass-dependent isotopic fractionations in several elements (e.g., O, Mg, Ca, Ti), large (~5-20‰) enrichments or depletions in neutron-rich isotopes (e.g., 48 Ca, 50 Ti, 54 Cr), and low inferred abundances of 26 Al ( 26 Al/ 27 Al < 1×10 −5 ). Understanding the origins of these features in FUN CAIs can shed light on the astrophysical environment and chemical processes that took place in the early Solar System. A large fraction (slightly less than 50%) of the ~20 FUN CAIs discovered so far are hibonite-rich (such as HAL, SHAL and DH-H1, collectively called HAL-type inclusions hereafter). According to their elemental and isotopic signatures and the results of evaporation experiments, HAL-type inclusions are thought to have formed as a distillation residue. However, questions regarding the timing of the formation of HAL-type inclusions (or FUN inclusions in general) relative to those of regular CAIs and the decoupling between the 26 Al abundances and nucleosynthetic anomalies remain poorly understood. In 2021, we reported the discovery of a new HAL-type inclusion, HIDALGO (Hibonite in Dar al Gani CO3) in the CO3 chondrite Dar al Gani 027 (DaG027), based on its (fractionated) oxygen isotopic compositions and low inferred 26 Al/ 27 Al ratio of (1.50±0.02)×10 −5 . Since then, more work on other short-lived and stable isotope systems and trace element abundances has been conducted. Here we report these new results and discuss the implications for the possible formation history of HIDALGO and origins of shortlived radionuclides (SLRs).

Meteorite↗

What Are the Olivine-Rich Boulders in the Upper Fan and Margin Unit at Jezero Crater, Mars?

Since February 2021, the Perseverance rover has explored Jezero Crater in the Nili Fossae region of Mars which hosts large outcrops of a regional olivine-carbonate unit. In the crater floor, Perseverance investigated two igneous formations: Máaz, composed of basaltic lava and/or pyroclastic flows, and Séítah, an olivine-rich cumulate] below Máaz. Then, Perseverance explored the western fan composed by diverse sedimentary rocks of variable composition, but often containing olivine On the upper fan and margin unit, Perseverance encountered number of centimetric to metric boulder rocks. Two main types of boulders were identified based on texture and composition: the olivine-rich and pyroxene-bearing boulders. Here, we use SuperCam data to describe the texture, geochemistry and mineralogy of the olivine-rich boulders. Then, we discuss their possible petrological origin and some possible implications for the regional Nili Fossae olivine-carbonate unit.

Mars 2020↗

A Coordinated Mineralogical and Oxygen Isotopic Study of Refractory Ca-Al-Rich Inclusions

Refractory Ca-Al-rich inclusions (CAIs) in primitive chondritic meteorites represent the oldest solids that formed in our Solar System. Coordinated analyses using multiple ion and electron-beam techniques are vital to fully understand complex nebular and asteroidal processes that CAIs may have experienced in the context of the formation and early evolution of our Solar System. We report the results of a coordinated mineralogical and oxygen isotopic study of unique grossite bearing CAIs from reduced CV (Vigarano type) carbonaceous chondrites using transmission electron microscopy and secondary ion mass spectrometry. Grossite (CaAl 4 O 7 ) occurs in cores of nodules in fine grained CAIs that likely represent aggregates of nebular condensates. In many occurrences, grossite has been partially replaced by hercynite [(Fe,Mg,Zn)Al 2 O 4 ], which displays complex microstructures and compositions, and magnetite nanoparticles. This grossite alteration likely occurred via crystallographically controlled metasomatic reactions with Zn, Fe-rich aqueous fluids on the parent asteroid. The constituent phases of grossite bearing CAIs show heterogeneous oxygen isotopic compositions . That is, grossite and perovskite are 16 O poor and melilite is variably 16 O-depleted in contrast to solar like, 16 O-rich hibonite and spinel. The observed oxygen isotopic distribution is interpreted as a result of mineralogically controlled oxygen isotopic exchange with an 16 O-poor fluid on the parent asteroid. Collectively, we conclude that the presence of limited fluids played an important role in preferential alteration of grossite to hercynite and magnetite and various degrees of 16 O depletion in grossite, perovskite, and melilite during thermal metamorphism on the CV chondrite parent asteroid.

Jangmi Han↗

Production of methane-rich syngas from hydrocarbon fuels using multi-functional catalyst/capture agent

The disclosure provides a gasification process for the production of a methane-rich syngas at temperatures exceeding 700.degree. C. through the use of an alkali hydroxide MOH, using a gasification mixture comprised of at least 0.25 moles and less than 2 moles of water for each mole of carbon, and at least 0.15 moles and less than 2 moles of alkali hydroxide MOH for each mole of carbon. These relative amounts allow the production of a methane-rich syngas at temperatures exceeding 700.degree. C. by enabling a series of reactions which generate H.sub.2 and CH.sub.4, and mitigate the reforming of methane. The process provides a methane-rich syngas comprised of roughly 20% (dry molar percentage) CH.sub.4 at temperatures above 700.degree. C., and may effectively operate within an IGFC cycle at reactor temperatures between 700-900.degree. C. and pressures in excess of 10 atmospheres.

09 BIOMASS FUELS↗

Methane-rich syngas production from hydrocarbon fuels using multi-functional catalyst/capture agent

The disclosure provides a gasification process for the production of a methane-rich syngas at temperatures exceeding 400.degree. C. through the use of an alkali hydroxide MOH, using a gasification mixture comprised of at least 0.25 moles and less than 2 moles of water for each mole of carbon, and at least 0.15 moles and less than 2 moles of alkali hydroxide MOH for each mole of carbon. These relative amounts allow the production of a methane-rich syngas at temperatures exceeding 400.degree. C. by enabling a series of reactions which generate H.sub.2 and CH.sub.4, and mitigate the reforming of methane. The process provides a methane-rich syngas comprised of roughly 20% (dry molar percentage) CH.sub.4 at temperatures above 400.degree. C., and may effectively operate within an IGFC cycle at reactor temperatures between 400-900.degree. C. and pressures in excess of 10 atmospheres.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Methods for growth of lithium-rich antiperovskite electrolyte films and use thereof

A process for preparing a lithium-rich antiperovskite electrolyte film involves forming a composite target of precursor metal oxide(s) and metal halide(s), and exposing the target to a pulsed laser beam under conditions suitable for depositing a film of lithium-rich antiperovskite on a surface. In some embodiments the process is used to prepare a film of Li.sub.3OCl from a target largely composed of Li.sub.2O and LiCl. Exposure of the target to a pulsed laser beam deposits antiperovskite electrolyte Li.sub.3OCl on a substrate. In another embodiment, sputtering may be used to prepare films of lithium-rich antiperovskites using the composite target of precursor metal oxide(s) and metal halide(s).

36 MATERIALS SCIENCE↗

Influences of temperature on permeability changes of flow-paths altered by highly alkaline Ca-rich groundwater - 15192

Fractures (or cracks) in host rock around the geological repository are considered as main flow-paths for the migration of radionuclides. Such fractures would be altered by the alkaline components (Ca, Na, K) leaching from cementitious materials for the construction of the repository. While silicate minerals in fractures are dissolved by highly alkaline groundwater, secondary minerals would deposit on the surface of fractures because of the reaction between the alkaline components and silicate species. The authors' previous study showed the generation of CSH-gel and the clogging of micro flow-path under the condition of Ca-rich and high pH by flow experiments. The present study examined the permeability changes with temperature in micro flow-path flowing highly alkaline Ca-rich solution, considering temperature at the depth of geological disposal system. For the simulation of micro flow-path such as fractures, 'micro flow-cell', which nipped a thin Teflon sheet with a slit between granite chip and Teflon basement, were used for the experiments. Highly alkaline Ca-rich solution (pH>12 and 8.5 mM Ca(OH){sub 2}) were injected into micro flow-cell with 2.0 ml/h of flow rate under the given temperature conditions (278 K, 296 K or 313 K). As a result, the permeability became lower with the increase in temperature. In addition, the deposition rates of CSH-gel became larger with the increase in temperature, and the activation energy was estimated to be 32.0 kJ/mol. These results suggest that flow-paths around the geological repository would undergo the clogging with CSH-gel in a shorter time-period under a condition of higher temperature. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Origin of Electrochemical Activation Leading to Enhanced Cycling Stability of Li‐ and Mn‐Rich Cathodes

Electrochemical activation is a critical step for optimal functioning of Li- and Mn-rich (LMR) cathodes, yet the underlying mechanism for such activation remains elusive. Here, by using scanning/transmission electron microscopy (S/TEM) combined with the associated energy-dispersive x-ray spectroscopy (EDS) and electron energy-loss spectroscopy (EELS), we decipher the origin of the activation enhanced electrochemical properties. We reveal that activation induces the formation of a spinel-like phase within the C2/m domains of the LMR cathode, where the transition-metal ions partially occupy both the tetrahedral (8a) and octahedral (16c) sites of the $Fd\bar{3}m$ spinel lattice, distinguishing the spinel-like phase from the conventional high-voltage spinel. Systematic varying the cycling voltage reveals a critical activation voltage above which this spinel-like phase forms, while lower voltages preserve the layered bulk structure. As the spinel-like phase is a stable structure for electrochemical cycling, the present findings provide direct mechanistic insight into the voltage-dependent activation process and explain how the C2/m to spinel-like transformation upon activation contributes to the electrochemical performance of LMR cathodes, providing guidance for the rational design of Li-rich cathodes with enhanced cycling durability.

Li-rich and Mn-rich cathode↗

Modifying Surface Chemistry to Enhance the Electrochemical Stability of Nickel‐Rich Cathode Materials

Residual impurities such as lithium carbonate and hydroxide are a major concern for accelerating parasitic reactions at the cathode electrolyte interface of lithium-ion batteries. Removal of these lithium-bearing species becomes a necessity for high-performance nickel-rich cathode materials. Instead of directly removing these impurities through washing steps, a wet impregnation process is employed to convert these detrimental surface impurities into beneficial surface coating on nickel-rich cathode materials. Specifically, the pristine cathode material is treated with Al(H 2 PO 4 ) 3 solution to convert undesired compounds into Li 3 PO 4 and AlPO 4 , both of which are considered positive surface coating materials for high-voltage cathodes. It is found that the introduced modification greatly suppresses the interfacial impedance hike and improves the capacity retention of the cathode material after repeating charging/discharging. It is believed that these benefits are realized through the modification of the surface chemistry of the cathode material, which helps to slow down the parasitic reactions and reduce the damage to the cathode material.

25 ENERGY STORAGE↗