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At least 1,081 records · Page 60

Microbial mats and the early evolution of life

Microbial mats have descended from perhaps the oldest and most widespread biological communities known. Mats harbor microbes that are crucial for studies of bacterial phylogeny and physiology. They illustrate how several oxygen-sensitive biochemical processes have adapted to oxygen, and they show how life adapted to dry land long before the rise of plants. The search for the earliest grazing protists and metazoa in stromatolites is aided by observations of mats: in them, organic compounds characteristic of ancient photosynthetic protists can be identified. Recent mat studies suggest that the 13C/12C increase observed over geological time in stromatolitic organic matter was driven at least in part by a long-term decline in atmospheric carbon dioxide levels.

NASA Center ARC↗

Oxygen redox activities governing high-voltage charging reversibility of Ni-rich layered cathodes

A schematic illustration indicative of the improved structural reversibility through stabilizing oxidized oxygen by Al doping. The chemical reactions and phase transitions at high voltages are generally considered to determine the electrochemical properties of high-voltage layered cathodes such as Ni-rich rhombohedral oxides. Even if significantly higher SOCs (states-of-charge) are utilized above the capability of transition metal redox (primarily Ni and Co), the effect of oxygen redox on Ni-rich rhombohedral oxides still looks mysterious thereby necessitating research that can clarify the relationship between redox reactions and phase transitions. Here, we performed a comprehensive and comparative study of the cationic and anionic redox reactions, as well as the structural evolution of a series of commercial Ni-rich layered oxides with and without Al doping. We combined the results from X-ray spectroscopy, operando electrochemical mass spectrometry, and neutron diffraction with electrochemical properties and thereby revealed the different oxygen redox activities associated with structural and electrochemical degradations. We reveal that Al doping suppresses the irreversible oxygen release but enhances the lattice oxygen oxidization. With this modulated oxygen redox activity, the Ni-rich layered oxides’ notorious H2–H3 structural phase transition becomes highly reversible. Our findings disentangle the different oxygen redox activities during high-voltage cycling and clarify the role of dopants in the Ni-rich layered oxides in terms of structural and electrochemical stability, shedding light on the future direction of optimizing layered cathode materials for safer high energy-density secondary batteries.

Lee, Gi-Hyeok↗

Domestication of Algae for Increasing Biomass Productivity

Microalgae cultivation processes have been developed for the production of a variety of bioproducts, however currently only a few species are used in commercial applications. Their domestication, that is strain improvements, is still in its infancy, with major advances required, specifically to maximize biomass productivity a limiting factor in microalgae production. This requires a deep understanding of algal biology, in particular to develop superior strains without the need of genetic technologies that would require lengthy regulatory permits, and often limit consumer acceptance. Adaptive Laboratory Evolution techniques, alone or in conjunction with sexual recombination, can allow for rapid develop of improved strains and their industrial production. Light harvesting antenna reduction has been a major approach to achieve increased photon utilization efficiency by cultures operating under full sunlight conditions due to higher light saturation levels, allowing for higher productivities under outdoor conditions. Decades of research yielded some promising results under controlled conditions with a few specific mutant strains. However, these failed to achieve the anticipated higher productivities in actual algal mass cultures, in part due to the inability of single mutations to overcome photoinhibition, reactive oxygen species, and other pleiotropic impacts on the complex metabolic processes of photosynthesis. Higher productivity strains will require multiple genetic improvements. We report on recent Adaptive Laboratory Evolution with the green alga Scenedesmus obliquus resulting in higher biomass productivity in open pond cultivation. Coupling our approach with sexual recombination and genome sequencing provides a path to algal domestication suitable for large-scale, low-cost biomass production.

09 BIOMASS FUELS↗

Paleoproterozoic snowball earth: extreme climatic and geochemical global change and its biological consequences

Geological, geophysical, and geochemical data support a theory that Earth experienced several intervals of intense, global glaciation ("snowball Earth" conditions) during Precambrian time. This snowball model predicts that postglacial, greenhouse-induced warming would lead to the deposition of banded iron formations and cap carbonates. Although global glaciation would have drastically curtailed biological productivity, melting of the oceanic ice would also have induced a cyanobacterial bloom, leading to an oxygen spike in the euphotic zone and to the oxidative precipitation of iron and manganese. A Paleoproterozoic snowball Earth at 2.4 Giga-annum before present (Ga) immediately precedes the Kalahari Manganese Field in southern Africa, suggesting that this rapid and massive change in global climate was responsible for its deposition. As large quantities of O(2) are needed to precipitate this Mn, photosystem II and oxygen radical protection mechanisms must have evolved before 2.4 Ga. This geochemical event may have triggered a compensatory evolutionary branching in the Fe/Mn superoxide dismutase enzyme, providing a Paleoproterozoic calibration point for studies of molecular evolution.

Earth (Planet)↗

Oxygen Vacancies in Niobium Pentoxide as a Source of Two-Level System Losses in Superconducting Niobium

We identify a major source of quantum decoherence in three-dimensional superconducting radio-frequency (SRF) resonators and two-dimensional transmon qubits composed of oxidized niobium: oxygen vacancies in the niobium pentoxide, which drive two-level system (TLS) losses. By probing the effect of sequential in situ vacuum-baking treatments on the rf performance of bulk Nb SRF resonators and on the oxide structure of a representative Nb sample using TOF SIMS, we find a nonmonotonic evolution of cavity quality factor Q0, which correlates with the interplay of Nb2O5 vacancy generation and oxide-thickness reduction. We localize this effect to the oxide itself and present the insignificant role of diffused interstitial oxygen in the underlying Nb by regrowing the oxide via wet oxidation, which reveals a mitigation of aggravated TLS losses. We hypothesize that such vacancies in the pentoxide serve as magnetic impurities and are a source of TLS-driven rf loss.

Bafia, Daniel P. [Fermilab]↗

Origin for electrochemically driven phase transformation in the oxygen electrode for a solid oxide cell

The next generation of fuel cells, electrolyzers, and batteries requires higher power, faster kinetics, and larger energy density, which necessitate the use of compositionally complex oxides to achieve multifunctionalities and activity. These compositionally complex oxides may change their phases and structures during an electrochemical process—a so-called “electrochemically driven phase transformation.” The origin for such a phase change has remained obscure. The aim of this paper is to present an experimental study and a theoretical analysis of phase evolution in praseodymium nickelates. Nickelate-based electrodes show up to 60 times greater phase transformation during operation when compared with thermally annealed ones. Theoretical analysis suggests that the presence of a reduced oxygen partial pressure at the interface between the oxygen electrode and the electrolyte is the origin for the phase change in an oxygen electrode. Guided by the theory, the addition of the electronic conduction in the interface layer leads to the significant suppression of phase change while improving cell performance and performance stability.

25 ENERGY STORAGE↗

Enhancing Metal‐Support Interactions of Ru Catalysts via Relaxation of Oxygen Vacancies for Hydrogen Production

The stability of Ru-based catalysts under harsh electrochemical conditions is a critical challenge limiting their practical application in energy conversion systems. In this study, Ru catalysts supported on ZrO 2-x , CeO 2-x , and ZrCeO 2-x are synthesized via pyrolysis of metal-organic frameworks (MOFs) and systematically evaluated to elucidate the role of support interactions on catalytic performance and durability. Advanced characterization techniques, including HR-TEM, XRD, XPS, and EXAFS, revealed that Ru-ZrCeO 2-x exhibited superior structural stability compared to Ru-ZrO 2-x and Ru-CeO 2-x , particularly under high-potential sweep (HPS) conditions. The incorporation of Ce into ZrO 2-x is shown to stabilize oxygen vacancies and enhance the interaction between Ru catalyst and the support, thereby mitigating catalyst degradation. Density functional theory (DFT) calculations further confirmed that Ce doping decreases formation energy of the oxygen vacancy, providing a thermodynamically favorable environment for Ru stabilization. This work demonstrates the promise of ZrCeO 2-x as a robust support material for Ru-based catalysts, advancing their potential for durable and efficient energy applications.

hydrogen evolution reaction↗

Reconstructing Oxygen-Deficient Zirconia with Ruthenium Catalyst on Atomic-Scale Interfaces toward Hydrogen Production

Downsizing a catalyst nanoparticle (NP) to a single atom (SA) has proven to be highly effective in increasing catalytic activity and decreasing the amount of catalyst required for various electrochemical reactions. However, insufficient stability of the single-atom site catalysts (SACs) is still a significant challenge for their practical application. Here, SACs firmly bound to stable metal oxide NPs are proposed to dramatically increase the electrochemical activity and stability of SA-based catalysts for hydrogen evolution reaction (HER). Starting from a Ru-infiltrated, Zr-based metal-organic framework (MOF), the tetragonal zirconium oxide (ZrO 2-x ) NPs-embedded carbon matrix is fabricated as support through facile pyrolysis. Simultaneously, Ru SAs as active sites are well dispersed on the surface of ZrO 2-x NPs due to the generation of oxygen vacancies in the tetragonal ZrO 2-x . Finally, the Ru-ZrO 2-x SAC exhibits a 4–5 times higher mass activity than commercial Pt and Ru catalysts and superior durability due to strong metal-support interaction (SMSI) between Ru atoms and ZrO 2-x substrate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evolution and use of combined mechanical and thermal codes for cryogenic turbopump bearings

Shaft bearing system analysis codes were developed, improved, and used to investigate Space Shuttle Main Engine (SSME) Liquid Oxygen (LOX) turbopump bearing problems, and to support the Marshall Space Flight Center Bearing and Seal Materials Test (BSMT) program. Thermal network modeling uses the SINDA thermal code, and the modeling of bearing quasi-dynamic characteristics uses the SHABERTH bearing/shaft code. These codes are solved concurrently for a bearing/shaft system using software developed for this purpose. Simulation of the SSME LOX turbopump turbine and pump end bearings and the MSFC BSMT operating in liquid nitrogen (LN sub 2) and LOX was done. The thermal network models include the bearing components, bearing carriers, shaft, housing, frictional heat, and viscous fluid energy. A cage model was included to account for heat generation between the cage and rolling elements. Since most bearing surfaces operate at temperatures well above the coolant saturation temperature, and move at high speed relative to the coolant, forced convection boiling is the dominant mechanism for heat removal. Improved modeling of forced convection film boiling was incorporated to take into account the local vapor generation at the high temperature surfaces. Rearing preloads in the pump and tester are provided by preload springs. As bearing operating clearances and contact angles change due to thermal effects and loading, the bearing preload changes with these varying conditions. These characteristics were modeled and are included in the overall system models. Results from these models indicate an operational limit which, if exceeded, predicts a thermal excursion.

Cody, Joe C.↗

[Petrological Analysis of Astrophysical Dust Analog Evolution]

This project "Petrological analysis of astrophysical dust analog evolution" was initiated to try to understand the vapor phase condensation, and the nature of the reaction products, in circumstellar environments, such as the solar nebula 4,500 Myrs ago, and in the interstellar medium. Telescope-based infrared [IR] spectroscopy offers a broad-scale inventory of the various types of dust in these environments but no details on small-scale variations in terms of chemistry and morphology and petrological phase relationships. Vapor phase condensation in these environments is almost certainly a non-equilibrium process. The main challenge to this research was to document the nature of this process that, based on astrophysical observations, seems to yield compositionally consistent materials. This observation may suggest a predictable character during non-equilibrium condensation. These astrophysical environments include two chemically distinct, that is, oxygen-rich and carbon-rich environments. The former is characterized by silicates the latter by carbon-bearing solids. According to cosmological models of stellar evolution circumstellar dust accreted into protoplanets wherein thermal and/or aqueous processes will alter the dust under initially, non-equilibrium conditions.

Rietmeijer, Frans J. M.↗

Oxygen vacancies in niobium pentoxide as a source of two-level system losses in superconducting niobium

Two-level systems (TLS) have long been a catch-all explanation for RF loss and quantum decoherence in superconducting devices. In our study, the first to directly link TLS losses to a specific physical mechanism, we demonstrate that oxygen vacancies in the naturally formed Nb₂O₅ on oxidized niobium are a major driver of such dissipation. We performed sequential in situ vacuum-baking treatments on niobium superconducting radio-frequency (SRF) cavities and used time-of-flight secondary ion mass spectrometry (TOF-SIMS) to reveal a nonmonotonic evolution in cavity quality factor (Q₀). This behavior correlates with the interplay of Nb₂O₅ vacancy generation and oxide-thickness dissolution. We localize this effect to the oxide itself and present the insignificant role of diffused interstitial oxygen in the underlying Nb by regrowing the oxide via wet oxidation, revealing a mitigation of aggravated TLS losses. We hypothesize that such vacancies in the pentoxide serve as magnetic impurities and are a source of TLS-driven rf loss. Although our measurements center on 3-D SRF cavities, the insights gained here have significant implications for mitigating decoherence in 2-D superconducting qubits.

Bafia, Daniel P. [Fermilab]↗

Study of advanced techniques for determining the long-term performance of components

A study was conducted of techniques having the capability of determining the performance and reliability of components for spacecraft liquid propulsion applications for long term missions. The study utilized two major approaches; improvement in the existing technology, and the evolution of new technology. The criteria established and methods evolved are applicable to valve components. Primary emphasis was placed on the propellants oxygen difluoride and diborane combination. The investigation included analysis, fabrication, and tests of experimental equipment to provide data and performance criteria.

Source record↗

Far Ultraviolet Astronomy

The Far Ultraviolet Spectroscopic Explorer (FUSE) is studying a wide range of astronomical problems in the 905-1187 Angstrom wavelength region through the use of high resolution spectroscopy. The FUSE bandpass forms a nearly optimal complement to the spectral coverage provided by the Hubble Space Telescope (HST), which extends down to approximately 1170 Angstroms. The photoionization threshold of atomic hydrogen (911 Angstroms) sets a natural short-wavelength limit for the FUV. FUSE was launched in June 1999 from Cape Canaveral, Florida, on a Delta II rocket into a 768 km circular orbit. Scientific observations started later that year. This spectral region is extremely rich in spectral diagnostics of astrophysical gases over a wide range of temperatures (100 K to over 10 million K). Important strong spectral lines in this wavelength range include those of neutral hydrogen, deuterium, nitrogen, oxygen, and argon (H I, D I, N I, O I, and Ar I), molecular hydrogen (H2), five-times ionized oxygen (O VI), and several ionization states of sulfur (S III - S VI). These elements are essential for understanding the origin and evolution of the chemical elements, the formation of stars and our Solar System, and the structure of galaxies, including our Milky Way. FUSE is one of NASA's Explorer missions and a cooperative project of NASA and the space agencies of Canada and France. These missions are smaller, more scientifically focused missions than the larger observatories, like Hubble and Chandra. FUSE was designed, built and operated for NASA by the Department of Physics and Astronomy at Johns Hopkins University. Hundreds of astronomers world-wide are using FUSE for a wide range of scientific research. Some of the important scientific discoveries from the first two years of the mission are described.

Sonneborn, George↗

Silicon Partitioning Between Iron-Rich Metal and Silicate Melt: New Constraints From Aerodynamic Laser Levitation Furnace Experiments

The partitioning of light elements (e.g., Si, C, H, etc.) between silicate melts and iron metal alloys as a function of pressure and temperature is a critical constraint in defining the compositional evolution of planetary interiors. While there are a significant number of experimental studies in the literature that examine the various influences of oxygen fugacity, temperature, pressure, and composition on the metal-melt partitioning of silicon, it is difficult to disentangle the effects of each variable due to the nominally independent parameters (e.g., pressure, temperature, composition) being collinear. To better test for the independent effects of pressure, temperature, and melt composition on the partitioning of silicon between iron alloy and silicate melt, new high temperature (1800°–2500°C), rapid quench (~700°C/s) aerodynamic levitation laser-heating experiments in the Fe-Si-Mg-O (En65-Fa5-Si3-Fe27) system were conducted. This high temperature, low pressure method is ideal for these experiments because it eliminates the metal container as a sink for elements of interest to partition into, and it has a rapid quench rate that minimizes potential exsolution of silicon from the metal phase during quench cooling. Given the short run times of the levitation experiments (30–60 seconds), a time series at a lower temperature (1700°C) in a vertical gas-mixing muffle tube furnace was also conducted to assess equilibrium times of the bulk composition. All successful runs were imaged using back-scatter electron imaging and analyzed for phase composition using a JEOL 8530F field emission microprobe. These new data were added to a comprehensive and internally consistent data set created from published experiments, and subsequently modeled using parameters designed to minimize collinearity (e.g., optical basicity is used as a proxy for melt composition). High collinearity is found in the data set however between temperature and oxygen fugacity, precluding any model that contains both as nominally independent variables. The resulting model demonstrates a statistically significant effect of pressure, temperature, and melt composition on the partitioning of silicon in Fe-rich metal, which has implications for the formation of planetary cores in rocky planets and provides important constraints on potential bulk core compositions.

Metal↗

Biological modulation of planetary atmospheres: The early Earth scenario

The establishment and subsequent evolution of life on Earth had a profound impact on the chemical regime at the planet's surface and its atmosphere. A thermodynamic gradient was imposed on near-surface environments that served as the driving force for a number on important geochemical transformations. An example is the redox imbalance between the modern atmosphere and the material of the Earth's crust. Current photochemical models predict extremely low partial pressures of oxygen in the Earth's prebiological atmosphere. There is widespread consensus that any large-scale oxygenation of the primitive atmosphere was contingent on the advent of biological (autotrophic) carbon fixation. It is suggested that photoautotrophy existed both as a biochemical process and as a geochemical agent since at least 3.8 Ga ago. Combining the stoichiometry of the photosynthesis reaction with a carbon isotope mass balance and current concepts for the evolution of the stationary sedimentary mass as a funion of time, it is possible to quantify, the accumulation of oxygen and its photosynthetic oxidation equivalents through Earth history.

Schidlowski, M.↗

Soft x-ray absorption spectroscopy and magnetic circular dichroism as operando probes of complex oxide electrolyte gate transistors

Electrolyte-based transistors utilizing ionic liquids/gels have been highly successful in the study of charge-density-controlled phenomena, particularly in oxides. Experimental probes beyond transport have played a significant role, despite challenges in their application in electric double-layer transistors. Here, we demonstrate the application of synchrotron soft x-ray absorption spectroscopy (XAS) and x-ray magnetic circular dichroism (XMCD) as operando probes of the charge state and magnetism in ion-gel-gated ferromagnetic perovskite films. Electrochemical response via oxygen vacancies at positive gate bias in LaAlO 3 (001)/La 0.5 Sr 0.5 CoO 3-δ is used as a test case. XAS/XMCD measurements of 4–25 unit-cell-thick films first probe the evolution of hole doping (from the O K-edge pre-peak) and ferromagnetism (at the Co L-edges), to establish a baseline. Operando soft XAS/XMCD of electrolyte-gated films is then demonstrated, using optimized spin-coated gels with a thickness of ~1 μm and a specific composition. The application of gate voltages up to +4 V is shown to dramatically suppress the O K-edge XAS pre-peak intensity and Co L-edge XMCD, thus enabling the Co valence and ferromagnetism to be tracked upon gate-induced reduction. Soft XAS and XMCD, with appropriate electrolyte design, are thus established to be viable for the operando characterization of electrolyte-gated oxides.

Yu, Biqiong↗

Solidification of carbon-oxygen white dwarfs

The internal structure of white dwarfs is discussed. Highly correlated plasmas are reviewed. Implications for phase separation in the core of cooling white dwarfs are considered. The consequences for evolution of white dwarfs are addressed.

Schatzman, E.↗

The origin and evolution of short-period Miras in the solar neighborhood: Constraints on the life cycle of old stars

The spatial distribution of the short-period (P less than 300 days) oxygen-rich Miras in the solar neighborhood can be fitted with an exponential scale height above the Galactic plane of about 600 pc. Using the Gliese catalog of local main-sequence stars, we estimate that the density of suitable G-type progenitor dwarfs within 20 pc of the Sun for these short-period Miras is 6 x 10(exp -4)/cu pc. The portion of the H-R diagram near the main-sequence turnoff of these velocity-selected Gliese stars is intermediate between that of the old open cluster NGC 188 and that of the metal-rich globular cluster, 47 Tuc. We infer that the main-sequence progenitors of the short-period Miras have masses near 1.0 solar mass, and we estimate that these Miras have ages approximately 9 x 10(exp 9). We also identify a few old disk red giants in the neighborhood of the Sun. On the basis of very limited information, we estimate that the total amount of mass lost from these stars during their first ascent up the red giant branch is less than or equal to 0.1 solar mass. We derive a duration of the short-period Mira phase of close to 5 x 10(exp 5) yr. This estimate for the duration of the short period Mira phase is longer than our estimate of 2 x 10(exp 5) yr for the duration of the Mira phase for stars with periods longer than 300 days. From their infrared colors, we estimate a typical mass-loss rate from the short-period Miras of approximately 1 x 10(exp -7) solar mass/yr.

Jura, M.↗