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At least 217 records · Page 12

An evolutionary system of mineralogy, Part VI: Earth’s earliest Hadean crust (> 4370 Ma)

Part VI of the evolutionary system of mineralogy catalogs 262 kinds of minerals, formed by 18 different processes, that we suggest represent the earliest solid phases in Earth’s crust. All of these minerals likely formed during the first tens of millions of years following the global-scale disruption of the Moon-forming impact prior to ~4.4 Ga, though no samples of terrestrial minerals older than ~4.37 Ga are known to have survived on Earth today. Our catalog of the earliest Hadean species includes 80 primary phases associated with ultramafic and mafic igneous rocks, as well as more than 80 minerals deposited from immiscible S-rich fluids and late-stage Si-rich residual melts. Earth’s earliest crustal minerals also included more than 200 secondary phases of these primary minerals that were generated by thermal metamorphism, aqueous alteration, impacts, and other processes. In particular, secondary mineralization related to pervasive near-surface aqueous fluids may have included serpentinization of mafic and ultramafic rocks, hot springs and submarine volcanic vent mineralization, hydrothermal sulfide deposits, zeolite and associated mineral formation in basaltic cavities, marine authigenesis, and hydration of subaerial lithologies. Additional Hadean minerals may have formed by thermal metamorphism of lava xenoliths, sublimation at volcanic fumaroles, impact processes, and volcanic lightning. These minerals would have occurred along with more than 180 additional phases found in the variety of meteorites that continuously fell to Earth’s surface during the early Hadean Eon.

Philosophy of mineralogy↗

Preliminary Results from the Saffire VI Experiment

Preliminary results are presented for one test of the last flight of the Spacecraft Fire Experiment (Saffire VI) which was conducted on an orbiting Cygnus spacecraft. These experiments directly address the risks associated with our understanding of spacecraft fire behavior at practical length scales and geometries. The lack of this experimental data has forced spacecraft designers to base their designs and safety precautions on 1-g understanding of flame spread, flame self-extinguishment, fire detection, and suppression. The Saffire experiment was developed by an international team of investigators with the goal of addressing open issues in spacecraft fire safety. NASA’s Spacecraft Fire Safety Demonstration Project was formulated with the goal of conducting a series of large-scale experiments in spacecraft environments that represent practical spacecraft fires. These tests spanned 1.5 to 3.2 kW with free air volumes of 17 to 19 cubic meters. The final flight in the series of six experiments examined concurrent spread over large samples (all 41 cm wide) including a thin sheet of flammable fuel (cotton/fiberglass 50 cm long); 2-sided spread over 1 cm thick polymethyl methacrylate (PMMA) (18 cm long); 1-sided spread over 0.5 cm thick (18 cm long); and Nomex fabric (7 cm long). Results are presented for the PMMA samples, the SIBAL sample, and the thin cotton samples from Saffire IV and V. The flame heat release is determined and compared to the overall temperature rise in the spacecraft and the change in the concentration of carbon dioxide and carbon monoxide in the spacecraft. Overall, the temperature and pressure rise in the spacecraft were found to be less significant than the increase in carbon dioxide and carbon monoxide.

fire↗

Preliminary Results from the Saffire VI Experiment

The preliminary results are presented for one test of the last flight of the Spacecraft Fire Experiment (Saffire VI) which was conducted on an orbiting Cygnus spacecraft. These experiments directly address the risks associated with our understanding of spacecraft fire behavior at practical length scales and geometries. The lack of this experimental data has forced spacecraft designers to base their designs and safety precautions on 1-g understanding of flame spread, flame self-extinguishment, fire detection, and suppression. The Saffire experiment was developed by an international team of investigators with the goal of addressing open issues in spacecraft fire safety. NASA’s Spacecraft Fire Safety Demonstration Project was designed with the goal of conducting a series of large-scale experiments in spacecraft environments that represent practical spacecraft fires. The final flight examined concurrent spread over large samples (all 41 cm wide) including a thin sheet of flammable fuel (cotton/fiberglass 50 cm long); 2-sided spread over 1 cm thick polymethyl methacrylate (PMMA) (18 cm long) ; 1-sided spread over 0.5 cm thick (18 cm long); and Nomex fabric (7 cm long). This paper focusses on the two-sided PMMA sample. The flame heat release is determined and is compared to the overall temperature rise in the spacecraft and the change in the concentration of carbon dioxide and carbon monoxide in the spacecraft.

fire↗

Activation of Low-Valent, Multiply M–M Bonded Group VI Dimers toward Catalytic Olefin Metathesis via Surface Organometallic Chemistry

Olefin metathesis is a broadly employed reaction with applications that range from fine chemicals to materials and petrochemicals. The design and investigation of olefin metathesis catalysts have been ongoing for over half a century, with advancements made in terms of activity, stability, and selectivity. Immobilization of organometallic complexes onto solid supports such as silica or alumina is a promising strategy for catalyst heterogenization, often resulting in increased activity and stability. Consequently, a broad range of early transition metal catalysts bearing alkyl, oxide/alkoxide, and amide ligands have been grafted onto silica and their reactivities investigated. In this paper, we report a series of silica-supported tungsten and molybdenum dimers (X 3 M≡MX 3, where M = W and Mo; X = neopentyl, tert-butoxide, and dimethyl amide) and their reactivities toward catalytic olefin metathesis. Dynamic nuclear polarization (DNP)-enhanced solid-state nuclear magnetic resonance (SSNMR), diffuse reflectance infrared Fourier transform (DRIFT), UV resonance Raman, and X-ray absorption (XAS) spectroscopies suggest that upon heterogenization the dimers bind to the surface in a monopodal fashion, with the M≡M triple bond remaining intact. These structural assignments were further corroborated by density functional theory (DFT) calculations. While the homogeneous dimer counterparts are inert, the supported low-valent alkyl W and Mo dimers become active for the disproportionative self-metathesis of propylene to ethylene and butenes and 4-nonene to 4-octene and 5-decene under mild conditions. The lack of activity observed for the free and supported tert-butoxide and dimethyl amide dimers likely suggests that the neopentyl groups are necessary for the formation of a putative alkylidene active species. The difference in reactivity between the free and supported dimers could be explained either by the lowering of the activation barrier of the complex through the electronic effects of the surface or by site isolation of catalytically relevant reactive intermediates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Using the “Inner” Array Boundary with KENO-VI [Slides]

Topics include: SGGP Array definition basics, what is meant by the "Inner" Boundary of an array, a critical experiment with flux filter, and NRC verification of criticality calculations with UNF-ST&DARDS.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Optimizing Alabama’s CO 2 Storage in Shelby County (Project OASIS) Milestone 6.0: Evaluation of Class VI Readiness

Introduction. Project OASIS is approximately 30 miles southeast of Birmingham, Alabama, and approximately 5 miles north-northwest of Alabama Power Company's Plant Gaston. Geologically, the Project area is in the Alabama fold and thrust belt province. This work builds on the initiatives of the Southeast Regional Carbon Utilization and Storage Acceleration Partnership (SECARB-USA, DE-FE0031830) that identified nearly 500 million metric tonnes of CO 2 emitted on an annual basis that is not collocated with prospective storage geology (the Coastal Plain of the Southeastern US in this context). This observation suggests costly investments in connective infrastructure (e.g., pipelines) or exploratory well drilling campaigns to identify CO 2 storage opportunities in under explored areas. While not traditionally thought of for saline storage, these studies suggest that storage prospects in the Valley and Ridge Province occur in relatively flat lying structural panels between thrust faults. For the Project OASIS region, available geologic studies related to hydrocarbon exploration suggest that Cambro-Ordovician carbonates and Cambrian clastic units offer multiple potential storage intervals, and that regional confining systems are present, such as the tectonically thickened Floyd-Parkwood Shale. The Project OASIS surface property is owned by a timber and land stewardship company, The Westervelt Company, Inc., who worked with the Project Team to select and prepare adequate sites for geologic assessment. The purpose of drilling the Westover Stratigraphic Test Well #2 was to collect geologic data to model the feasibility of commercial scale CO 2 injection and storage in an under explored region. This initiative benefits the regions emitters as the data generated from this study can inform their own internal decision making. The field program included geological and geophysical evaluations, reservoir engineering analyses, and risk assessments. This report evaluates existing data, as well as a variety of modeling scenarios to evaluate project readiness. Importantly, the impact of this study is not limited to Alabama as there are numerous large emitters throughout Appalachia, in similar geologic settings, contemplating their decarbonization options.

20 FOSSIL-FUELED POWER PLANTS↗

The Unexpected Role of Se VI Species in Epoxidations with Benzeneseleninic Acid and Hydrogen Peroxide

Abstract Benzeneperoxyseleninic acid has been proposed as the key intermediate in the widely used epoxidation of alkenes with benzeneseleninic acid and hydrogen peroxide. However, it reacts sluggishly with cyclooctene and instead rapidly decomposes in solution to a mixed selenonium–selenonate salt that was identified by X‐ray absorption and 77 Se NMR spectroscopy, as well as by single crystal X‐ray diffraction. This process includes a selenoxide elimination of the peroxyseleninic acid with liberation of oxygen and additional redox steps. The salt is relatively stable in the solid state, but generates the corresponding selenonic acid in the presence of hydrogen peroxide. The selenonic acid is inert towards cyclooctene on its own; however, rapid epoxidation occurs when hydrogen peroxide is added. This shows that the selenonic acid must first be activated through further oxidation, presumably to the heretofore unknown benzeneperoxyselenonic acid. The latter is the principal oxidant in this epoxidation.

Sands, Kai N.↗

The Unexpected Role of Se VI Species in Epoxidations with Benzeneseleninic Acid and Hydrogen Peroxide

Abstract Benzeneperoxyseleninic acid has been proposed as the key intermediate in the widely used epoxidation of alkenes with benzeneseleninic acid and hydrogen peroxide. However, it reacts sluggishly with cyclooctene and instead rapidly decomposes in solution to a mixed selenonium–selenonate salt that was identified by X‐ray absorption and 77 Se NMR spectroscopy, as well as by single crystal X‐ray diffraction. This process includes a selenoxide elimination of the peroxyseleninic acid with liberation of oxygen and additional redox steps. The salt is relatively stable in the solid state, but generates the corresponding selenonic acid in the presence of hydrogen peroxide. The selenonic acid is inert towards cyclooctene on its own; however, rapid epoxidation occurs when hydrogen peroxide is added. This shows that the selenonic acid must first be activated through further oxidation, presumably to the heretofore unknown benzeneperoxyselenonic acid. The latter is the principal oxidant in this epoxidation.

Sands, Kai N.↗

Localized corrosion: Passive film breakdown vs. Pit growth stability, Part VI: Pit dissolution kinetics of different alloys and a model for pitting and repassivation potentials

Here, the pitting resistance of SS316L, SS304, SS430, and pure Fe was studied in chloride-containing solution. Among these alloys, SS316L exhibits the highest pit initiation rate, but also the highest pitting potential. To explain this phenomenon, the maximum pit dissolution current density (i diss,max ) of the alloys in saturated pit solution was measured using one-dimensional artificial pit electrodes. A lower i diss,max was found to correlate with higher pitting and repassivation potentials. Based on a recently proposed pitting framework, a conceptual model for pitting and repassivation potentials was established, based on which the effect of i diss,max on pitting resistance was discussed.

one-dimensional artificial pit electrode↗