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At least 379 records · Page 21

Thermal stability of hexagonal OsB{sub 2}

The synthesis of novel hexagonal ReB{sub 2}-type OsB{sub 2} ceramic powder was performed by high energy ball milling of elemental Os and B powders. Two different sources of B powder have been used for this mechanochemical synthesis. One B powder consisted of a mixture of amorphous and crystalline phases and a mixture of {sup 10}B and {sup 11}B isotopes with a fine particle size, while another B powder was a purely crystalline (rhombohedral) material consisting of enriched {sup 11}B isotope with coarse particle size. The same Os powder was used for the synthesis in both cases. It was established that, in the first case, the hexagonal OsB{sub 2} phase was the main product of synthesis with a small quantity of Os{sub 2}B{sub 3} phase present after synthesis as an intermediate product. In the second case, where coarse crystalline {sup 11}B powder was used as a raw material, only Os{sub 2}B{sub 3} boride was synthesized mechanochemically. The thermal stability of hexagonal OsB{sub 2} powder was studied by heating under argon up to 876 °C and cooling in vacuo down to −225 °C. During the heating, the sacrificial reaction 2OsB{sub 2}+3O{sub 2}→2Os+2B{sub 2}O{sub 3} took place due to presence of O{sub 2}/water vapor molecules in the heating chamber, resulting in the oxidation of B atoms and formation of B{sub 2}O{sub 3} and precipitation of Os metal out of the OsB{sub 2} lattice. As a result of such phase changes during heating, the lattice parameters of hexagonal OsB{sub 2} changed significantly. The shrinkage of the a lattice parameter was recorded in 276–426 °C temperature range upon heating, which was attributed to the removal of B atoms from the OsB{sub 2} lattice due to oxidation followed by the precipitation of Os atoms and formation of Os metal. While significant structural changes occurred upon heating due to presence of O{sub 2}, the hexagonal OsB{sub 2} ceramic demonstrated good phase stability upon cooling in vacuo with linear shrinkage of the lattice parameters and no phase changes detected during cooling. - Graphical abstract: The in situ high temperature XRD contour plot (A) and XRD patterns (B) of h-OsB{sub 2} upon heating and cooling under an argon atmosphere. - Highlights: • Different boron sources were compared for the synthesis of h-OsB{sub 2}. • The phase stability and thermal behavior of h-OsB{sub 2} were studied by in situ XRD. • Shrinkage of the a lattice parameter was observed from 276 °C to 426 °C upon heating. • Oxidation of OsB{sub 2} produced B vacancies led to the shrinkage of a lattice parameter.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Hybrid Line List for CH4 and Hot Methane Continuum

Molecular line lists (a catalogue of transition frequencies and line strengths) are important for modelling absorption and emission processes in atmospheres of different astronomical objects, such as cool stars and exoplanets. In order to be applicable for high temperatures, line lists for molecules like methane must contain billions of transitions, which makes their direct (line-by-line) application in radiative transfer calculations impracticable. Here we suggest a new, hybrid line list format to mitigate this problem, based on the idea of temperature-dependent absorption continuum. Methods. The line list is partitioned into a large set of relatively weak lines and a small set of important, stronger lines. The weaker lines are then used either to construct a temperature-dependent (but pressure-independent) set of intensity cross sections or are blended into a greatly reduced set of super-lines. The strong lines are kept in the form of temperature independent Einstein A coefficients. Results. A line list for methane is constructed as a combination of 17 million strong absorption lines relative to the reference absorption spectra and a background methane continuum in two temperature-dependent forms, of cross sections and super-lines. This approach eases the use of large high temperature line lists significantly as the computationally expensive calculation of pressure dependent profiles only need to be performed for a relatively small number of lines. Both the line list and cross sections were generated using a new 34 billion methane line list (34 to10), which extends the 10to10 line list to higher temperatures (up to 2000 K). The new hybrid scheme can be applied to any large line lists containing billions of transitions. We recommend to use super-lines generated on a high resolution grid based on resolving power R = 1,000,000 to model the molecular continuum as a more flexible alternative to the temperature dependent cross sections.

Line Profiles↗

Analysis of WRF extreme daily precipitation over Alaska using self‐organizing maps

Abstract We analyze daily precipitation extremes from simulations of a polar‐optimized version of the Weather Research and Forecasting (WRF) model. Simulations cover 19 years and use the Regional Arctic System Model (RASM) domain. We focus on Alaska because of its proximity to the Pacific and Arctic oceans; both provide large moisture fetch inland. Alaska's topography also has important impacts on orographically forced precipitation. We use self‐organizing maps (SOMs) to understand circulation characteristics conducive for extreme precipitation events. The SOM algorithm employs an artificial neural network that uses an unsupervised training process, which results in finding general patterns of circulation behavior. The SOM is trained with mean sea level pressure (MSLP) anomalies. Widespread extreme events, defined as at least 25 grid points experiencing 99th percentile precipitation, are examined using SOMs. Widespread extreme days are mapped onto the SOM of MSLP anomalies, indicating circulation patterns. SOMs aid in determining high‐frequency nodes, and hence, circulations are conducive to extremes. Multiple circulation patterns are responsible for extreme days, which are differentiated by where extreme events occur in Alaska. Additionally, several meteorological fields are composited for nodes accessed by extreme and nonextreme events to determine specific conditions necessary for a widespread extreme event. Individual and adjacent node composites produce more physically reasonable circulations as opposed to composites of all extremes, which include multiple synoptic regimes. Temporal evolution of extreme events is also traced through SOM space. Thus, this analysis lays the groundwork for diagnosing differences in atmospheric circulations and their associated widespread, extreme precipitation events.

Glisan, Justin M.↗

Zirconium Oxycarbide: A Highly Stable Catalyst Material for Electrochemical Energy Conversion

Abstract Metal carbides and oxycarbides have recently gained considerable interest due to their (electro)catalytic properties that differ from those of transition metals and that have potential to outperform them as well. The stability of zirconium oxycarbide nanopowders (ZrO 0.31 C 0.69 ), synthesized via a hybrid solid‐liquid route, is investigated in different gas atmospheres from room temperature to 800 °C by using in‐situ X‐ray diffraction and in‐situ electrical impedance spectroscopy. To feature the properties of a structurally stable Zr oxycarbide with high oxygen content, a stoichiometry of ZrO 0.31 C 0.69 has been selected. ZrO 0.31 C 0.69 is stable in reducing gases with only minor amounts of tetragonal ZrO 2 being formed at high temperatures, whereas it decomposes in CO 2 and O 2 gas atmosphere. From online differential electrochemical mass spectrometry measurements, the hydrogen evolution reaction (HER) onset potential is determined at −0.4 V RHE . CO 2 formation is detected at potentials as positive as 1.9 V RHE as ZrO 0.31 C 0.69 decomposition product, and oxygen is anodically formed at 2.5 V RHE , which shows the high electrochemical stability of this material in acidic electrolyte. This peopwery makes the material suited for electrocatalytic reactions at anodic potentials, such as CO and alcohol oxidation reactions, in general.

Chemistry↗

Enhanced lithium ion transport in garnet-type solid state electrolytes

Al-substituted Li 7 La 3 Zr 2 O 12 samples processed under argon show enhanced Li-ion transport and interfacial properties in symmetrical cells with lithium electrodes, compared to those prepared in air. In particular, the samples prepared under argon have higher ionic conductivities and lower interfacial impedances in symmetrical lithium cells, and show better DC cycling characteristics. The electronic conductivities are also somewhat higher. Pellets subjected to thermal treatment under the two types of atmospheres have different colors but exhibit similar microstructures. X-ray diffraction experiments suggest that there are slight structural differences between the two types of samples, but few dissimilarities were observed in elemental composition, distribution of ions, oxidation states, or bond lengths using laser-induced breakdown spectroscopy (LIBS), x-ray photoelectron spectroscopy (XPS), and extended x-ray absorption fine structure spectroscopy (EXAFS) to analyze the materials. Additionally, there was no evidence that La or Zr were reduced during the processing under Ar. Possible explanations for the improved electrochemical properties of the sample prepared under Ar compared to the one prepared in air include differences in grain boundary chemistries and conductivities and/or a small concentration of oxygen vacancies in the former.

25 ENERGY STORAGE↗

Differences in spore size and atmospheric survival shape stark contrasts in the dispersal dynamics of two closely related fungal pathogens

A frequently ignored but critical aspect of microbial dispersal is survival in the atmosphere. Here, we exposed spores of two closely related, morphologically dissimilar, and economically important fungal pathogens to typical atmospheric environments and modeled their movement in the troposphere. Alternaria solani conidia are nearly 10 times larger than A. alternata conidia, but in our experiments, most died within 24 h, while over half of A. alternata conidia remained viable on day 12. Next, we modeled the movement of spores across North America. We predict 99% of the larger A. solani conidia settle within 24 h, with a maximum dispersal distance of 100 km. By contrast, most A. alternata conidia remain airborne for more than 12 days, and dispersal over long distances(2000 km) is likely. Counterintuitively, the larger A. solani conidia survive poorly, as compared to smaller A. alternata conidia, but also land sooner and move over shorter distances.

59 BASIC BIOLOGICAL SCIENCES↗

Fast-current-heating devices to study in situ phase formation in metallic glasses by using high-energy synchrotron radiation

Details of fast-resistive-heating setups, controlled heating ranging from ~10 1 K s –1 to ~10 3 K s –1 , to study in situ phase transformations (on heating and on cooling) in metallic glasses by high-energy synchrotron x-ray diffraction are discussed here. Both setups were designed and custom built at the Leibniz Institute for Solid State and Materials Research Dresden (IFW Dresden) and have been implemented at the P02.1 Powder Diffraction and Total Scattering Beamline and the P21.1 Swedish Materials Science Beamline at PETRA III storage ring, DESY, Hamburg. The devices are interchangeable at both beamlines. Joule heating is triggered automatically and is timed with the incident beam and detector. The crystallization process can be controlled via a feedback circuit by monitoring the change in the time-dependent resistivity and temperature of glasses. Different ambient atmospheres, such as vacuum and inert gases (He and Ar), can be used to control oxidation and cooling. The main focus of these devices is on understanding the crystallization mechanism and kinetics in metallic glasses, which are brittle and for which fast heating gives defined glass–crystal composites with enhanced plasticity. As an example, phase-transformation sequence(s) in a prototyped Cu–Zr-based metallic glass is described on heating, and a crystalline phase beneficial to the plasticity is identified.

47 OTHER INSTRUMENTATION↗

Starspot distributions on fully convective M dwarfs: Implications for radial velocity planet searches

Since M4.5–M9 dwarfs exhibit equatorial rotation velocities of the order of 10 km s{sup −1} on average, radial velocity surveys targeting this stellar population will likely need to find methods to effectively remove starspot jitter. We present the first high resolution Doppler images of the M4.5 dwarf, GJ 791.2A, and the M9 dwarf, LP 944-20. The time series spectra of both objects reveal numerous line profile distortions over the rotation period of each star, which we interpret as starspots. The transient distortions are modeled with spot/photosphere contrast ratios that correspond to model atmosphere temperature differences of T{sub phot}−T{sub spot} = 300 and 200 K. GJ 791.2A is a fully convective star with v sin i = 35.1 km s{sup −1}. Although we find more starspot structure at high latitudes, we reconstruct spots at a range of phases and latitudes with a mean spot filling of ∼3%. LP 944-20 is one of the brightest known late-M dwarfs, with spectral type M9V and v sin i = 30.8 km s{sup −1}. Its spectral time series exhibits two dominant transient line distortions that are reconstructed as high latitude spots, while a mean spot filling factor of only 1.5% is found. The occurrence of low-contrast spots at predominantly high latitudes, which we see in both targets here, is, in general, likely to be responsible for the low amplitude photometric variability seen in late-M dwarfs. For GJ 791.2A, the radial velocities induced by the starspot features yield an rms velocity variability of 138 m s{sup −1}, which can be reduced by a factor of 1.9 using our reconstructed surface brightness distributions.

79 ASTRONOMY AND ASTROPHYSICS↗

Developing a simulator-based satellite dataset for using machine learning techniques to derive aerosol-cloud-precipitation interactions in models and observations in a consistent framework

Aerosol-cloud-precipitation interactions (ACPI) remain a major uncertainty in understanding the Earth’s radiation budget and water cycle (including extremes). After decades of active research, various observationally based metrics have been developed to constrain ACPI in Earth System Models (ESMs), but direct comparison of model and data estimates can confound scientific understanding because limitations and uncertainties in sampling and retrieval procedures may combine with model deficiencies in process representations of ACPI to obstruct understanding. Furthermore, conventional ACPI metrics often vary from one regime to another, and the ACPI process representation in ESMs is also typically derived based on only a limited area/regime (even though the parameterization applies globally). To bridge the gap between models and data and to correctly describe ACPI in all regimes, we propose to construct a new CALIPSO-CloudSat merged dataset that is produced by the same algorithms used in satellite simulators in ESMs, and to use machine learning techniques to derive new ACPI metrics that can be accurately estimated by satellites and can provide meaningful constraints on cloud microphysical process representations in ESMs. The dataset will include measured and retrieved variables for aerosol, cloud, and precipitation from CALIPSO and CloudSat, and environmental variables from meteorological reanalysis. The data will be used to train a neural network to construct the ACPI metrics as a function of environmental conditions. The new ACPI formula will be used to constrain the ACPI in the Energy Exascale Earth System Model (E3SM), and to augment/reformulate the ACPI process representation in the E3SM to improve the simulation of the evolution of the atmosphere under different environmental conditions.

54 ENVIRONMENTAL SCIENCES↗

Advanced monitoring of soil-vegetation co-dynamics reveals the successive controls of snowmelt on soil moisture and on plant seasonal dynamics in a mountainous watershed

Evaluating the interactions between above- and below-ground processes is important to understand and quantify how ecosystems respond differently to atmospheric forcings and/or perturbations and how this depends on their intrinsic characteristics and heterogeneity. Improving such understanding is particularly needed in snow-impacted mountainous systems where the complexity in water and carbon storage and release arises from strong heterogeneity in meteorological forcing and terrain, vegetation and soil characteristics. This study investigates spatial and temporal interactions between terrain, soil moisture, and plant seasonal dynamics at the intra- and inter-annual scale along a 160 m long mountainous, non-forested hillslope-to-floodplain system in the upper East River Watershed in the upper Colorado River Basin. To this end, repeated UAV-based multi-spectral aerial imaging, ground-based soil electrical resistivity imaging, and soil moisture sensors were used to quantify the interactions between above and below-ground compartments. Results reveal significant soil-plant co-dynamics. The spatial variation and dynamics of soil water content and electrical conductivity, driven by topographic and soil intrinsic characteristics, correspond to distinct plant types, with highest plant productivity in convergent areas. Plant productivity in heavy snow years benefited from more water infiltration as well as a shallow groundwater table depth. In comparison, low snowpack years with an early first bare-ground date, which are linked to an early increase in plant greenness, imply a short period of saturated conditions that leads to lower average and maximum greenness values during the growing season. Overall, these results emphasize the strong impact of snowpack dynamics, and terrain and subsurface characteristics on the heterogeneity in plant type and seasonal dynamics.

54 ENVIRONMENTAL SCIENCES↗

Influences of emission sources and meteorology on aerosol chemistry in a polluted urban environment: results from DISCOVER-AQ California

Abstract. The San Joaquin Valley (SJV) in California experiences persistent air-quality problems associated with elevated particulate matter (PM) concentrations due to anthropogenic emissions, topography, and meteorological conditions. Thus it is important to unravel the various sources and processes that affect the physicochemical properties of PM in order to better inform pollution abatement strategies and improve parameterizations in air-quality models. During January and February 2013, a ground supersite was installed at the Fresno–Garland California Air Resources Board (CARB) monitoring station, where comprehensive, real-time measurements of PM and trace gases were performed using instruments including an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and an Ionicon proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS) as part of the NASA Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) campaign. The average submicron aerosol (PM1) concentration was 31.0 µg m−3 and the total mass was dominated by organic aerosols (OA, 55 %), followed by ammonium nitrate (35 %). High PM pollution events were commonly associated with elevated OA concentrations, mostly from primary sources. Organic aerosols had average atomic oxygen-to-carbon (O / C), hydrogen-to-carbon (H / C), and nitrogen-to-carbon (N / C) ratios of 0.42, 1.70, and 0.017, respectively. Six distinct sources of organic aerosol were identified from positive matrix factorization (PMF) analysis of the AMS data: hydrocarbon-like OA (HOA; 9 % of total OA, O / C = 0.09) associated with local traffic, cooking OA (COA; 18 % of total OA, O / C = 0.19) associated with food cooking activities, two biomass burning OA (BBOA1: 13 % of total OA, O / C = 0.33; BBOA2: 20 % of total OA, O / C = 0.60) most likely associated with residential space heating from wood combustion, and semivolatile oxygenated OA (SV-OOA; 16 % of total OA, O / C = 0.63) and low-volatility oxygenated OA (LV-OOA; 24 % of total OA, O / C = 0.90) formed via chemical reactions in the atmosphere. Large differences in aerosol chemistry at Fresno were observed between the current campaign (winter 2013) and a previous campaign in winter 2010, most notably that PM1 concentrations were nearly 3 times higher in 2013 than in 2010. These variations were attributed to differences in the meteorological conditions, which influenced primary emissions and secondary aerosol formation. In particular, COA and BBOA concentrations were greater in 2013 than 2010, where colder temperatures in 2013 likely resulted in increased biomass burning activities. The influence from a nighttime formed residual layer that mixed down in the morning was found to be much more intense in 2013 than 2010, leading to sharp increases in ground-level concentrations of secondary aerosol species including nitrate, sulfate, and OOA, in the morning between 08:00 and 12:00 PST. This is an indication that nighttime chemical reactions may have played a more important role in 2013. As solar radiation was stronger in 2013 the higher nitrate and OOA concentrations in 2013 could also be partly due to greater photochemical production of secondary aerosol species. The greater solar radiation and larger range in temperature in 2013 also likely led to both SV-OOA and LV-OOA being observed in 2013 whereas only a single OOA factor was identified in 2010.

54 ENVIRONMENTAL SCIENCES↗

Globular-cluster stars - Results of theoretical evolution and pulsation studies compared with the observations.

Survey of recently published studies on globular clusters, and comparison of stellar evolution and pulsation theory with reported observations. The theory of stellar evolution is shown to be capable of describing, in principle, the behavior of a star through all quasi-static stages. Yet, as might be expected, estimates of bulk properties obtained by comparing observations with results of pulsation and stellar atmosphere theory differ somewhat from estimates of these same properties obtained by comparing observations with results of evolution theory. A description is given of how such estimates are obtained, and suggestions are offered as to where the weak points in each theory may lie.

Iben, I., Jr.↗

Vertical shear in the Jovian equatorial zone.

Jupiter photographs taken in two different wavelength regions (blue and red) are studied for clues to differing Jovian atmosphere motions. The relative motions of features visible on these photographs may be interpreted as a vertical shear at visible cloud level. The value obtained implies that the north equatorial zone must be about 0.35 deg K warmer than the adjacent equatorial zone. Deeper in the atmosphere the reverse must hold.

Layton, R. G.↗

Our present state of ignorance of the outer planets and their satellites.

Although the outer solar system contains the bulk of the angular momentum of the system and a huge fraction of the total planetary mass, very little is actually known about it. Massive Jupiter, with its low mean density and huge red spot (possibly a Taylor column), shows a complex rotational pattern as a result of three rotating systems, each having a different period. Atmospheric scattering of the reflected solar radiation makes spectral interpretation uncertain. Imprecisions in the Bond albedo cause discrepancies between actual and predicted solar energy absorbed. Saturn is similar to Jupiter in massiveness, low density, atmospheric aerosols, and albedo. Its rings are believed to be largely water ice. To date, no evidence of radiation belts, analogous to Jupiter's, exists for Saturn, Uranus, or Neptune. Methane and hydrogen have been detected in the atmospheres of all these planets, but the mole fraction of hydrogen is lower in the atmospheres of Uranus and Neptune. Uranus' 98 degree inclination will provide basis for study of its atmospheric circulation. Our knowledge of Pluto is restricted to the sparsest physical data.

Rea, D. G.↗