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At least 1,081 records · Page 60

Measuring Sodium Chloride Contents of Aerosols

Amount of sodium chloride in individual aerosol particles measured in real time by analyzer that includes mass spectrometer. Analyzer used to determine mass distributions of active agents in therapeutic or diagnostic aerosols derived from saline solutions and in analyzing ocean spray. Aerosol particles composed of sodium chloride introduced into oven, where individually vaporized on hot wall. Vapor molecules thermally dissociated, and some of resulting sodium atoms ionized on wall. Ions leave oven in burst and analyzed by spectrometer, which is set to monitor sodium-ion intensity.

Sinha, M. P.↗

Quantifying the Diversity of an Atmospheric Aerosol Population in an Arctic Oil Field on a Single‐Particle Level

As the Arctic rapidly warms, sea ice extent is decreasing and oil and gas extraction activities are expanding. Local combustion emissions affect the Arctic atmospheric aerosol chemical mixing state (the distribution of chemical species across the aerosol population), which impacts climate-relevant properties. Bulk and single-particle measurements of submicron aerosols were conducted at Oliktok Point, Alaska within the North Slope of Alaska oil fields. In this work, we quantify aerosol diversity using online single-particle mass spectrometry data (32,880 individual particles), offline single-particle microscopy data (20,912 individual particles), and online bulk aerosol mass spectrometry and aethalometer data. This method was used to derive individual particle mass fractions for both refractory and non-refractory material within distinct particle types. Single-particle, average single-particle, and bulk population diversities (D i , D α , D γ , respectively) and mixing state indices (χ) were calculated for the data set. Calculated D i values were generally low (2.2 ± 0.6), as individual particle masses were dominated by a few chemical species of interest. Aged aerosol particles (those internally mixed with nitrate and/or sulfate) exhibited higher D i values (>3) compared to recently emitted (fresh) aerosol particles. During oil field plume periods, D α values approached three due to the abundance of diesel combustion particles, which were rich in sulfate, black carbon, and organic aerosol. Overall, the submicron aerosol population within the Arctic oil fields was found to be relatively externally mixed (χ < 50%), due to the constant local emissions within oil fields combining with background aerosol and locally emitted sea spray aerosol at the coastal site.

Wu, J.↗

Creep and rupture of an ODS alloy with high stress rupture ductility

The creep and stress rupture properties of an oxide (Y2O3) dispersion strengthened nickel-base alloy, which also is strengthened by gamma-prime precipitates, was studied at 760 and 1093 C. At both temperatures, the alloy YDNiCrAl exhibits unusually high stress rupture ductility as measured by both elongation and reduction in area. Failure was transgranular, and different modes of failure were observed including crystallographic fracture at intermediate temperatures and tearing or necking almost to a chisel point at higher temperatures. While the rupture ductility was high, the creep strength of the alloy was low relative to conventional gamma prime strengthened superalloys in the intermediate temperature range and to ODS alloys in the higher temperature range. These findings are discussed with respect to the alloy composition; the strengthening oxide phases, which are inhomogeneously dispersed; the grain morphology, which is coarse and elongated and exhibits many included grains; and the second phase inclusion particles occurring at grain boundaries and in the matrix. The creep properties, in particular the high stress dependencies and high creep activation energies measured, are discussed with respect to the resisting stress model of creep in particle strengthened alloys.

Mcalarney, M. E.↗

The Feasibility of Multipole Electrostatic Radiation Shielding

Although passive shielding appears to be the only workable solution for galactic cosmic radiation (GCR), active shielding may play an important augmenting role to control the dose from solar particle events (SPEs). It has been noted that, to meet the guidelines of NCRP Report No. 98 through the six SPEs of 1989, a crew member would need roughly double the passive shielding that is necessary to control the GCR dose . This would dramatically increase spacecraft mass, and so it has been proposed that a small but more heavily shielded storm shelter may be used to protect the crew during SPEs. Since a gradual SPE may last 5 or more days, staying in a storm shelter may be psychologically and physiologically distressing to the crew. Storm shelters do not provide shielding for the spacecraft itself against the SPE radiation, and radiation damage to critical electronics may result in loss of mission and life. Single-event effects during the radiation storm may require quick crew response to maintain the integrity of the spacecraft, and confining the crew to a storm shelter prohibits their attending to the spacecraft at the precise time when that attention is needed the most. Active shielding cannot protect against GCR because the particle energies are too high. Although lower energy particles are easier to stop in a passive shield, such shielding is more satisfactory against GCR than against SPE radiation because of the tremendous difference in their initial fluences. Even a small fraction of the SPE fluence penetrating the passive shielding may result in an unacceptably high dose. Active shielding is more effective than passive shielding against SPE radiation because it offers 100% shielding effectiveness up to the cutoff energy, and significant shielding effectiveness beyond the cutoff as well.

Metzger, Philip T.↗

Voyager observations of O(+6) and other minor ions in the solar wind

The plasma science (PLS) experiments on the Voyager 1 and 2 spacecraft began making measurements of the solar wind shortly after the two launches in the fall of 1977. In reviewing the data obtained prior to the Jupiter encounters in 1979, we have found that the large dynamic range of the PLS instrument generally allows a clean separation of signatures of minor ions (about 2.5% of the time) during a single instrument scan in energy per charge. The minor ions, most notably O(+6), are well separated from the protons and alpha particles during times when the solar wind Mach number (ratio of streaming speed to thermal speed) is greater than approximately 15. During the Earth to Jupiter cruise we find that the average ratio of alpha particle number density to that of oxygen is 66 +/- 7 (Voyager 1) and 71 +/- 17 (Voyager 2). These values are consistent with the value 75 +/- 20 inferred from the Ion Composition Instrument on ISEE 3 during the period spanning 1978 and 1982. We have inferred an average coronal temperature of (1.7 +/- 0.1) x 10(exp 6) K based on the ratio of O(+7) to O(+6) number densities. Our observations cover a period of increasing solar activity. During this time we have found that the alpha particle to proton number density ratio is increasing with the solar cycle, the oxygen to proton ratio increases, and the alpha particle to oxygen ratio remains relatively constant in time.

Villanueva, Louis↗

Analysis of the pre-flight and post-flight calibration procedures performed on the Liulin space radiation dosimeter

Liulin, a dosimetry-radiometry system, was developed to satisfy the requirements for active flux and dose rate measurements for the flight of the second Bulgarian cosmonaut in 1988. The system consists of a compact battery-operated silicon solid state detector unit and a read/write microcomputer and telemetry unit. We describe the pre-flight calibrations with charged particles, using radioactive sources and accelerated 170 MeV/nucleon proton and alpha particles at the Dubna, Russia cyclotron. We discuss comparisons with data obtained on Mir with the French-built tissue equivalent LET spectrometer NAUSICAA. Lastly, we describe post-flight calibrations performed with 1 GeV/nucleon 56Fe ions at the Brookhaven National Laboratory AGS accelerator, where the instrument was mounted in tandem with several thin position-sensitive silicon detectors behind a stopping target. The silicon detectors provided an energy spectrum for the surviving charged nuclear fragments for which the flux and absorbed dose were recorded by Liulin.

long duration↗

Ultrahigh temperature in situ transmission electron microscopy based bicrystal coble creep in Zirconia II: Interfacial thermodynamics and transport mechanisms

This work uses a combination of stress dependent single grain boundary Coble creep and zero-creep experiments to measure interfacial energies, along with grain boundary point defect formation and migration volumes in cubic ZrO 2 . These data, along with interfacial diffusivities measured in a companion paper are then applied to analyzing two-particle sintering. The analysis presented here indicates that the large activation volume, v * = v f + v m primarily derives from a large migration volume and suggests that the grain boundary rate limiting defects are delocalized, possibly due to electrostatic interactions between charge compensating defects. The discrete nature of the sintering and creep process observed in the small-scale experiments supports the hypothesis that grain boundary dislocations serve as sources and sinks for grain boundary point defects and facilitate strain during sintering and Coble creep. Model two-particle sintering experiments demonstrate that initial-stage densification follows interface reaction rate-limited kinetics.

36 MATERIALS SCIENCE↗

Understanding how single-atom site density drives the performance and durability of PGM-free Fe–N–C cathodes in anion exchange membrane fuel cells

One of the most important needs for the future of low-cost fuel cells is the development of highly active platinum group metal (PGM)-free catalysts. For the oxygen reduction reaction, Fe–N–C materials have been widely studied in both acid and alkaline media. However, reported catalysts in the literature show quite different intrinsic activity and in-cell performance, despite similar synthesis routes and precursors. Here, two types of Fe–N–C are prepared from the same precursor and procedure – the main difference is how the precursor was handled prior to use. It is shown that in one case Fe overwhelmingly existed as highly active single-metal atoms in FeN4 coordination (preferred), while in the other case large Fe particles coexisting with few single metal atoms were obtained. As a result, there were drastic differences in the catalyst structure, activity, and especially in their performance in an operating anion exchange membrane fuel cell (AEMFC). Additionally, it is shown that catalyst layers created from single-atom-dominated Fe–N–C can have excellent performance and durability in an AEMFC using H 2 /O 2 reacting gases, achieving a peak power density of 1.8 W cm -2 – comparable to similar AEMFCs with a Pt/C cathode – and being able to operate stably for more than 100 h. Finally, the Fe–N–C cathode was paired with a low-loading PtRu/C anode electrode to create AEMFCs (on H 2 /O 2 ) with a total PGM loading of only 0.135 mg cm -2 (0.090 mg Pt cm -2 ) that was able to achieve a very high specific power of 8.4 W mg PGM -1 (12.6 W mg Pt< sup>-1 ).

36 MATERIALS SCIENCE↗

Slow manifolds of classical Pauli particle enable structure-preserving geometric algorithms for guiding center dynamics

Since variational symplectic integrators for the guiding center was proposed, structure-preserving geometric algorithms have become an active research field in plasma physics. We found that the slow manifolds of the classical Pauli particle enable a family of structure-preserving geometric algorithms for guiding center dynamics with long-term stability and accuracy. This discovery overcomes the difficulty associated with the unstable parasitic modes for variational symplectic integrators when applied to the degenerate guiding center Lagrangian. It is a pleasant surprise that Pauli's Hamiltonian for electrons, which predated the Dirac equation and marks the beginning of particle physics, reappears in classical physics as an effective algorithm for solving an important plasma physics problem. This technique is applicable to other degenerate Lagrangians reduced from regular Lagrangians.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

A subauroral and mid-latitude view of substorm activity

Experimental observations from a variety of sources made during a substorm period near 0900 UT on January 2, 1971 have provided evidence confirming mid-latitude and subauroral phenomena associated with magnetic substorm activity. A review of these observations, including ground and balloon observations made near L=4 at the conjugate stations Siple, Antarctica and Roberval, Canada and data obtained from the synchronous-orbit satellite ATS 5 positioned about 2 hours west of the Siple, Roberval meridian, is presented. During the hour before the reported correlated bursts of X rays and VLF noise (Rosenberg et al., 1971), the plasmapause appears to be displaced towards the equator from Siple; resonance conditions along the field lines at Siple were favorable for the observation of results of magnetospheric wave-particle interactions involving electrons with energies exceeding 30 keV. The correlated observations are a potential source of information concerning the relationship of ULF and VHF noise activity to the magnetospheric particle population at middle latitudes; the injection and subsequent drift of low and medium energy electrons during substorms; and enhanced particle precipitation deep within the plasmasphere during substorms.

Carpenter, D. L.↗

Fog dispersion

A study of economically viable techniques for dispersing warm fog at commercial airports is presented. Five fog dispersion techniques are examined: evaporation suppression, downwash, mixing, seeding with hygroscopic material, thermal techniques, and charged particle techniques. Thermal techniques, although effective, were found to be too expensive for routine airport operations, and detrimental to the environment. Seeding or helicopter downwash are practical for small-scale or temporary fog clearing, but are probably not useful for airport operations on a routine basis. Considerable disagreement exists on the capability of charged particle techniques, which stems from the fact that different assumptions and parameter values are used in the analytical models. Recommendations resulting from the review of this technique are listed, and include: experimental measurements of the parameters in question; a study to ascertain possible safety hazards, such as increased electrical activity or fuel ignition during refueling operations which could render charged particle techniques impractical; and a study of a single charged particle generator.

Frost, W.↗

Interplanetary shocks preceded by solar filament eruptions

The solar and interplanetary characteristics of six interplanetary shock and energetic particle events associated with the eruptions of solar filaments lying outside active regions are discussed. The events are characterized by the familiar double-ribbon H-alpha brightenings observed with large flares, but only very weak soft X-ray and microwave bursts. Both impulsive phases and metric type II bursts are absent in all six events. The energetic particles observed near the earth appear to be accelerated predominantly in the interplanetary shocks. The interplanetary shock speeds are lower and the longitudinal extents considerably less than those of flare-associated shocks. Three of the events were associated with unusual enhancements of singly-ionized helium in the solar wind following the shocks. These enhancements appear to be direct detections of the cool filament material expelled from the corona. It is suggested that these events are part of a spectrum of solar eruptive events which include both weaker events and the large flares. Despite their unimpressive and unreported solar signatures, the quiescent filament eruptions can result in substantial space and geophysical disturbances.

Cane, H. V.↗

Engineering Active Sites of Metal/Metal Oxide Catalysts by Oxide Ligand Overlayers

Abstract Engineering sites of supported metal catalysts is essential to enhancing activity and selectivity. Such enhancement is typically achieved by particle size modification, surface alloying, or attaching molecular ligands. Yet, control strategies for complex, multifunctional molecules and catalysts, where selectivity is crucial, are lacking. Here, we demonstrate that submonolayer WO x with tunable coverage preferentially decorates well‐coordinated Pt terrace sites as a stable ligand. By combining experimental kinetics with probe molecules, in situ spectroscopies, and first‐principles modeling, we show that the WO x coverage on Pt modifies the metal‐to‐acid site balance while retaining the acid strength intact and results in optimal reactivity for metal‐acid catalyzed reactions at a specific metal, size, and support‐dependent WO x coverage. The oxide can also alter the reactant adsorption mode, reversing selectivity and pathways from terrace‐ to step‐dominated, as evidenced in furfural decarbonylation and hydrogenation. The insights open avenues for improving metal/metal oxide catalysts beyond the specific system.

Zhou, Jiahua↗

Differentiating supported platinum single atoms, clusters and nanoparticles by styrene hydrogenation

Supported metal catalysts often consist of metal sites ranging from nanoparticles to subnanometer clusters and single atoms. It remains a necessity to differentiate these sites to guide design of optimal catalysts. Here we report a simple method to assess the distribution of metal active sites in catalyst samples. The method takes the advantage of the structure sensitivity of styrene hydrogenation over titania supported platinum (Pt) catalysts with Pt aggregates varied from single atom to ~1.40 nm nanoparticles. The physicochemical properties were characterized by STEM, XPS, XANES, H2-TPR and CO-chemisorption measurements. The reactivity of Pt sites was quantified by styrene hydrogenation at ambient conditions. The nanometer-sized Pt clusters have significantly higher activity than Pt nanoparticles, sub-nanometer clusters or isolated single atoms. Additionally, the relationship between activity and structural/electronic properties of Pt sites influenced by particle sizes was discussed. Similar relationship was found in the carbon supported Pt catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cross-Scale Catalyst Modeling Applied to H 2 Storage and Release via Formic Acid

Here, we propose the Systems-to-Atoms (S2A) modeling framework that integrates the kinetics of reaction chemistry and structural configurations across various length scales with the aim of establishing a versatile template for multiscale modeling of reactive flow problems and to predict the operando activity of catalyst materials. The approach encompasses a microkinetic model to analyze surface reactions on individual facets of catalyst nanoparticles coupled with the computation of average surface reaction rates for catalyst nanoparticles of specific size distributions. Macro-homogeneous surface reaction kinetics are derived as a function of catalyst loading and used as input parameters for the continuum-scale reactor model. The cross-scale framework enables the optimization of catalyst utilization through reactor design and operating strategy. To demonstrate the framework, we studied the storage and release of hydrogen from formic acid, a promising liquid organic hydrogen carrier (LOHC), over Pd, Pt, and Cu catalysts. The framework predicts observed trends in formic acid dehydrogenation activity for catalysts with comparable weight loadings and metal particle diameters, demonstrating satisfactory quantitative alignment. Finally, the seamless transmission of parameter uncertainties between scales is also discussed.

08 HYDROGEN↗

Disordered, Sub-Nanometer Ru Structures on CeO 2 are Highly Efficient and Selective Catalysts in Polymer Upcycling by Hydrogenolysis

We report non-degradable polyolefin plastics pose severe environmental threats, and thus demand efficient upcycling technologies. In this work, we discovered that low-loading (= 0.25 wt%) Ru/CeO 2 exhibits remarkable catalytic performance in the hydrogenolysis of polypropylene (PP), polyethylene (PE), and n-C 16 H 34 that is superior to high-loading (= 0.5 wt%) Ru/CeO 2 . They possess high PP conversion efficiency (7-fold increase over current literature reports), low selectivity towards undesired CH 4 , and good isomerization ability. In the low-loading range, the intrinsic activity of Ru in PP hydrogenolysis increases as the particle size decreases, opposite of the trend in the high-loading range. Detailed characterization revealed that the abrupt changes in catalytic behaviors coincide with Ru species transitioning from well-defined to highly disordered structures in the low-loading domain. The disordered Ru species were shown to be sub-nanometer in size and cationic. Mechanistically, the regioselectivity and the rate dependence on hydrogen pressure of C-C bond cleavage are different on low- and high-loading Ru/CeO 2 , both explained by the higher coverage of adsorbed hydrogen (*H) on low-loading Ru/CeO 2 . This work uncovers the remarkable catalytic performance of highly disordered, sub-nanometer, cationic Ru species in polyolefin hydrogenolysis, opening immense opportunities to develop effective, selective, and versatile catalysts for plastic upcycling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Viral but not bacterial community successional patterns reflect extreme turnover shortly after rewetting dry soils

As central members of soil trophic networks, viruses have the potential to drive substantial microbial mortality and nutrient turnover. Pinpointing viral contributions to terrestrial ecosystem processes remains a challenge, as temporal dynamics are difficult to unravel in the spatially and physicochemically heterogeneous soil environment. In Mediterranean grasslands, the first rainfall after seasonal drought provides an ecosystem reset, triggering microbial activity during a tractable window for capturing short-term dynamics. In this report we simulated precipitation in microcosms from four distinct dry grassland soils and generated 144 viromes, 84 metagenomes and 84 16S ribosomal RNA gene amplicon datasets to characterize viral, prokaryotic and relic DNA dynamics over 10 days. Vastly different viral communities in each soil followed remarkably similar successional trajectories. Wet-up triggered a significant increase in viral richness, followed by extensive compositional turnover. Temporal succession in prokaryotic communities was much less pronounced, perhaps suggesting differences in the scales of activity captured by viromes (representing recently produced, ephemeral viral particles) and total DNA. Still, differences in the relative abundances of Actinobacteria (enriched in dry soils) and Proteobacteria (enriched in wetted soils) matched those of their predicted phages, indicating viral predation of dominant bacterial taxa. Rewetting also rapidly depleted relic DNA, which subsequently reaccumulated, indicating substantial new microbial mortality in the days after wet-up, particularly of the taxa putatively under phage predation. Production of abundant, diverse viral particles via microbial host cell lysis appears to be a conserved feature of the early response to soil rewetting, and results suggest the potential for ‘Cull-the-Winner’ dynamics, whereby viruses infect and cull but do not decimate dominant host populations.

54 ENVIRONMENTAL SCIENCES↗

Genotype-Specific Neutralization of Norovirus Is Mediated by Antibodies Against the Protruding Domain of the Major Capsid Protein

Abstract Human noroviruses are the most common viral agents of acute gastroenteritis. Recently, human intestinal enteroids were shown to be permissive for norovirus infection. We tested their suitability as a system to study norovirus neutralization. Hyperimmune sera raised against virus-like particles (VLPs) representing different genotypes showed highly specific neutralization activity against GII.4 and GII.6 noroviruses. Carbohydrate blocking assays and neutralization exhibited similar patterns in antibody responses. Notably, sera produced against chimeric VLPs that presented swapped structural shell and protruding (P) domains, from different genotypes showed that neutralization is primarily mediated by antibodies mapping to the P domain of the norovirus capsid protein. This study provides empirical information on the antigenic differences among genotypes as measured by neutralization, which could guide vaccine design.

Ford-Siltz, Lauren A.↗