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At least 109 records · Page 6

Snow Albedo Feedbacks Enhance Snow Impurity-Induced Radiative Forcing in the Sierra Nevada

This study employs a fully coupled meteorology-chemistry-snow model to investigate the impacts of light-absorbing particles (LAPs) on snow darkening in the Sierra Nevada. After comprehensive evaluation with spatially and temporally complete satellite retrievals, the model shows that LAPs in snow reduce snow albedo by 0.013 (0-0.045) in the Sierra Nevada during the ablation season (April-July), producing a midday mean radiative forcing (RF) of 4.5 W m -2 which increases to 15-22 W m -2 in July. LAPs in snow accelerate snow aging processes and reduce snow cover fraction, which doubles the albedo change and radiative forcing caused by LAPs. The impurity-induced snow darkening effects decrease snow water equivalent and snow depth by 20 mm and 70 mm in June in Sierra Nevada bighorn sheep habitat. The earlier snowmelt reduces root zone soil moisture by 20%, deteriorating the forage productivity and playing a negative role in the survival of bighorn sheep.

54 ENVIRONMENTAL SCIENCES↗

Cellular solidification of transparent monotectics

Understanding how liquid phase particles are engulfed or pushed during freezing of a monotectic is addressed. The additional complication is that the solid-liquid interface is nonplanar due to constitutional undercooling. Some evidence of particle pushing where the particles are the liquid phase of the montectic was already observed. Cellular freezing of the succinonitrile-glycerol system also occurred. Only a few compositions were tested at that time. The starting materials were not especially pure so that cellular interface observed was likely due to the presence of unkown impurities, the major portion of which was water. Topics addressed include: the effort of modeling the particle pushing process using the computer, establishing an apparatus for the determination of phase diagrams, and the measurement of the temperature gradients with a specimen which will solidify on the temperature gradient microscope stage.

Kaulker, W. F.↗

Energy Evaluation of Electron Beam Treatment of Perfluoroalkyl Substances in Water: A Critical Review

Due to their recalcitrant nature and ubiquitous use, per- and polyfluoroalkyl substances (PFAS) will continue to be major water treatment hurdles. Although effective water treatment technologies exist for physical removal of many PFAS from water (e.g., activated carbon and ion-exchange resin), a PFAS-concentrated waste stream is generated as an end product that can potentially reintroduce PFAS back into the environment. Thus, there is an increased interest in developing destructive technologies to decompose and mineralize PFAS directly in water or in these waste streams. High energy electron beam (e-beam) accelerators have been used for water treatment to degrade a wide range of recalcitrant contaminants, including PFAS, since the 1960s. However, large-scale applications of e-beam for water treatment are restricted due to its high energy consumption and inability to treat large flow rates. Considering there are very few available technologies for destructive removal of PFAS, this study provides a critical review on the treatment of PFAS by direct irradiation of contaminated water by e-beam from an energy consumption point of view. To date, very limited studies have been conducted to investigate the success of this technology to treat PFAS. Results from the limited studies were not directly comparable due to the variation in operating conditions and water quality parameters used in the studies. Here, for the first time, we develop and apply the concept of electrical energy per order (EE/O) to assess the performance of e-beam for PFAS treatment. Results show that EE/O is a better performance parameter than the G value of e-beam for interstudy comparisons and to evaluate the effects of water quality and operating parameters on e-beam performance. We additionally developed a kinetic scheme to predict the performance of e-beam to treat PFAS and revealed that the competition between species to react with aqueous electrons is the determinant factor influencing PFAS degradation efficiency. Comparison of EE/O values of e-beam (range: 31–176 kWh m –3 order –1 ) with other destructive technologies (range: 5–9595 kWh m –3 order –1 ) suggest that e-beam, for PFAS treatment, is a promising approach under favorable conditions. Furthermore, this review further elucidates the feasibility and limitations of e-beam technology that could be improved upon to potentially make e-beam viable for large-scale water treatment applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Comparative Genomic Analysis of Three Pseudomonas Species Isolated from the Eastern Oyster (Crassostrea virginica) Tissues, Mantle Fluid, and the Overlying Estuarine Water Column

The eastern oysters serve as important keystone species in the United States, especially in the Gulf of Mexico estuarine waters, and at the same time, provide unparalleled economic, ecological, environmental, and cultural services. One ecosystem service that has garnered recent attention is the ability of oysters to sequester impurities and nutrients, such as nitrogen (N), from the estuarine water that feeds them, via their exceptional filtration mechanism coupled with microbially-mediated denitrification processes. It is the oyster-associated microbiomes that essentially provide these myriads of ecological functions, yet not much is known on these microbiota at the genomic scale, especially from warm temperate and tropical water habitats. Among the suite of bacterial genera that appear to interplay with the oyster host species, pseudomonads deserve further assessment because of their immense metabolic and ecological potential. To obtain a comprehensive understanding on this aspect, we previously reported on the isolation and preliminary genomic characterization of three Pseudomonas species isolated from minced oyster tissue (P. alcaligenes strain OT69); oyster mantle fluid (P. stutzeri strain MF28) and the water collected from top of the oyster reef (P. aeruginosa strain WC55), respectively. In this comparative genomic analysis study conducted on these three targeted pseudomonads, native to the eastern oyster and its surrounding environment, provided further insights into their unique functional traits, conserved gene pools between the selected pseudomonads, as well as genes that render unique characteristics in context to metabolic traits recruited during their evolutionary history via horizontal gene transfer events as well as phage-mediated incorporation of genes. Moreover, the strains also supported extensively developed resistomes, which suggests that environmental microorganisms native to relatively pristine environments, such as Apalachicola Bay, Florida, have also recruited an arsenal of antibiotic resistant gene determinants, thus posing an emerging public health concern.

Pathak, Ashish↗

Oxidation Kinetics of Chemically Vapor-Deposited Silicon Carbide in Wet Oxygen

The oxidation kinetics of chemically vapor-deposited SiC in dry oxygen and wet oxygen (P(sub H2O) = 0.1 atm) at temperatures between 1200 C and 1400 C were monitored using thermogravimetric analysis. It was found that in a clean environment, 10% water vapor enhanced the oxidation kinetics of SiC only very slightly compared to rates found in dry oxygen. Oxidation kinetics were examined in terms of the Deal and Grove model for oxidation of silicon. It was found that in an environment containing even small amounts of impurities, such as high-purity Al2O3 reaction tubes containing 200 ppm Na, water vapor enhanced the transport of these impurities to the oxidation sample. Oxidation rates increased under these conditions presumably because of the formation of less protective sodium alumino-silicate scales.

Opila, Elizabeth J.↗

Effects of Mineral Impurities and Heat on Uranium(VI) Sorption onto Bentonite (Final Report)

Most nuclear waste disposal options include compacted bentonite, consisting of montmorillonite clay, as part of a barrier system to minimize contaminant mobility. Uranium (U) is the primary element in spent nuclear fuel, and from an environmental perspective, a potential contaminant of water resources. Furthermore, uranium may control nuclear fuel degradation rates and the consequent release of other radioactive contaminants based on its diffusive transport away from waste canisters. Uranium sorption onto clay and other mineral surfaces is expected to limit U(VI) mobility in these systems. However, at this point a prediction of U(VI) sorption and transport behavior in performance assessment (PA) models is complicated by a series of factors, such as: (1) the presence of various U(VI) solution species with different charges and sorption characteristics; (2) the complex microstructure of montmorillonite clay resulting in two types of clay porosities and multiple sorption sites; (3) the largely unknown effects of bentonite mineral impurities on pore water chemistry, U(VI) sorption and diffusion behavior; and (4) the potential impacts of heat, generated by the decay of spent fuel, on mineralogical and microstructural transformations, and any subsequent effects on radionuclide sorption and mobility. In this project, we investigated the effects of calcite impurities on U(VI) sorption and diffusion onto montmorillonite before and after mineral exposure to heat. Overall, our main goals were to: 1. Gain a mechanistic understanding of the effects of calcite impurities on U(VI) sorption and diffusion in montmorillonite/bentonite at variable chemical conditions, and before and after mineral exposure to heat; and to 2. Work towards the development of new surface complexation and diffusion models to predict U(VI) sorption and mobility in montmorillonite/bentonite while accounting for the impacts of calcite impurities and heat. In order to achieve these goals, we pursued the following research objectives and tasks: 1. Characterize the effects of calcite impurities on U(VI) sorption onto Na-montmorillonite, and evaluate if and how these effects change due to solids’ exposure to heat (Task 1). 2. Characterize U(VI) surface speciation in solid samples from Task 1, with a particular focus on U(VI) precipitates and co-precipitates (Task 2). 3. Test the relevance of observed changes in U(VI) sorption characteristics for U(VI) diffusive transport behavior in bentonite barriers (Task 3). 4. Evaluate the exclusion of anionic U(VI) solution complexes from clay nanopores (Task 4). 5. Building on Tasks 1-4, start the development of new surface complexation and reactive transport models that can simulate and predict U(VI) sorption and diffusion in complex bentonite systems (Task 5). A detailed description of all tasks, and their specific results and conclusions is provided in this report.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Multi-discipline resource inventory of soils, vegetation and geology

The author has identified the following significant results. Computer classification of natural vegetation, in the vicinity of Big Summit Prairie, Crook County, Oregon was carried out using MSS digital data. Impure training sets, representing eleven vegetation types plus water, were selected from within the area to be classified. Close correlations were visually observed between vegetation types mapped from the large scale photographs and the computer classification of the ERTS data (Frame 1021-18151, 13 August 1972).

Simonson, G. H.↗

Adhesion of impure ice on surfaces

The undesirable buildup of ice can compromise the operational safety of ships in the Arctic to high-flying airplanes, thereby having a detrimental impact on modern life in cold climates. The obstinately strong adhesion between ice and most functional surfaces makes ice removal an energetically expensive and dangerous affair. Hence, over the past few decades, substantial efforts have been directed toward the development of passive ice-shedding surfaces. Conventionally, such research on ice adhesion has almost always been based on ice solidified from pure water. However, in all practical situations, freezing water has dissolved contaminants; ice adhesion studies of which have remained elusive thus far. Here, in this work, we cast light on the fundamental role played by various impurities (salt, surfactant, and solvent) commonly found in natural water bodies on the adhesion of ice on common structural materials. We elucidate how varying freezing temperature & contaminant concentration can significantly alter the resultant ice adhesion strength making it either super-slippery or fiercely adherent. The entrapment of impurities in ice changes with the rate of freezing and ensuing adhesion strength increases as the cooling temperature decreases. We discuss the possible role played by the in situ generated solute enriched liquid layer and the nanometric water-like disordered ice layer sandwiched between ice and the substrate behind these observations. Our work provides useful insights into the elementary nature of impure water-to-ice transformation and contributes to the knowledge base of various natural phenomena and rational design of a broad spectrum of anti-icing technologies for transportation, infrastructure, and energy systems.

36 MATERIALS SCIENCE↗

Process for purification of waste water produced by a Kraft process pulp and paper mill

The water from paper and pulp wastes obtained from a mill using the Kraft process is purified by precipitating lignins and lignin derivatives from the waste stream with quaternary ammonium compounds, removing other impurities by activated carbon produced from the cellulosic components of the water, and then separating the water from the precipitate and solids. The activated carbon also acts as an aid to the separation of the water and solids. If recovery of lignins is also desired, then the precipitate containing the lignins and quaternary ammonium compounds is dissolved in methanol. Upon acidification, the lignin is precipitated from the solution. The methanol and quaternary ammonium compound are recovered for reuse from the remainder.

Humphrey, M. F.↗

Ganymede, Europa, Callisto, and Saturn's rings - Compositional analysis from reflectance spectroscopy

The reflectance spectra of Ganymede, Europa, Callisto, and the rings of Saturn are analyzed, using laboratory reflectance studies of water, frost, ice, and mineral mixtures. It is found that the spectra of the icy Galilean satellites are characteristic of water ice, or frost on ice, rather than pure water frost; and that the decrease in reflectance at visible wavelengths is caused by other mineral grains on the surface. The spectra of Saturn's rings are more characteristic of water frost, with other mineral grains mixed in the frost but not on the surface. It is also found that impurities of all these objects are not in isolated patches, but intimately mixed with the water. A new absorption feature at 1.15 microns has been identified in Ganymede, Callisto, and possibly Europa, which cannot be seen in Saturn's rings and whose cause is unknown.

Clark, R. N.↗

Molecular dynamics simulations of uranyl and plutonyl cations in a task-specific ionic liquid

Ionic liquids (ILs) are a unique class of solvents with potential applications in advanced separation technologies relevant to the nuclear industry. ILs are salts with low melting points and a wide range of tunable physical properties, such as viscosity, hydrophobiciy, conductivity, and liquidus range. ILs have negligible vapor pressure, are often non-flammable, and can have high thermal stability and a wide electrochemical window, making them attractive for use in separations processes relevant to the nuclear industry. Metal salts generally have a low solubility in ILs; however, by incorporating new functional groups into the IL cation or anion that promote complexation with the metal, the solubility can be greatly increased. One such task-specific ionic liquid (TSIL) is 1-carboxy-N, N, N-trimethylglycine bis(trifluoromethylsulfonyl)imide ([Hbet][Tf 2 N]). Water, which is detrimental for electrochemical separations, is a common impurity in ILs and can coordinate with actinyl cations, particularly in ILs containing only weakly coordinating components. Understanding the behavior of actinides in TSIL/water mixtures on a molecular level is vital for designing improved separations processes. Classical molecular dynamics simulations of uranyl(VI) and plutonyl(VI) in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][Tf 2 N]) with deprotonated Hbet (betaine) and water have been performed to understand the coordination and dynamics of the actinyl cations. We find that betaine is a much stronger ligand than water and prefers to coordinate the metal in a bidentate manner. Potential of mean force simulations yield a relative free energy for betaine coordination of approximately -120 to -90 kJ/mol in mixtures with water. As the amount of betaine coordinated to the actinide increases, the diffusion coefficient of the actinyl cation decreases. Moreover, the betaine ligand is able to bridge between two metal centers, resulting in dimeric complexes with actinide–actinide distances of ~5 Å. Potential of mean force simulations show that these structures are stable, with relative free energies of up to -40 kJ/mol. The crystal structure for [(UO 2 ) 2 (bet) 6 (H 2 O) 2 ][Tf 2 N] 4 shows that the betaine bridges between two uranium atoms to form dimeric complexes similar to those found in our simulations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impurity Levels in Cerium Oxide Microspheres Prepared by Internal Gelation Sol-Gel Methods

Impurity levels were measured in cerium oxide microspheres fabricated by modified internal gelation sol-gel methods. A combination of glow discharge mass spectrometry, electron impact mass spectrometry, combustion gas analysis and instrumental gas analysis were used to assess a wide range of potential elemental impurities. Low concentrations of carbon, nitrogen, and hydrogen impurities in microspheres showed a dependence on how microspheres were washed. Silicon impurities are believed to derive from silicone oil used during sol-gel processing. Spheres washed by the preferred approach had impurity levels below 100 ppm for all elements tested. For applications such as nuclear fuels, sol-gel methods could meet purity specifications as long as metal nitrate feed solutions of sufficient purity are used and microspheres are washed appropriately. In this study, cerium was used as a surrogate for plutonium-238, which is used in radioisotope power systems as a heat source, to determine whether carbon or other impurities were concentrated during internal gelation processing and remained after heat treatments. Analyses indicated low concentrations of impurities in cerium oxide microspheres after sintering steps that were well below documented limits for plutonium-238 oxide fuels. Modified washing methods, combined with a pressurized water treatment, resulted in sintered cerium oxide sol-gel microspheres with low impurity levels.

cerium oxide, sol-gel, internal gelation, microsph↗

Self-deactivation of water vapor - Role of the dimer

A phenomenological multiple-relaxation theory of the deactivation rate constant for the nu-2 (1 - 0) bending mode of water vapor is presented which incorporates the role not only of the excited monomer but also of the bound molecular complex, in particular the dimer. The deactivation takes place by means of three parallel processes: (1) collisional deexcitation of the excited monomer, (2) a two-step reaction involving association and spontaneous redissociation of an H2O collision complex, and (3) spontaneous dissociation of the stably bound H2O dimer. Oxygen, but not nitrogen or argon, serves as an effective chaperon for the formation of the activated complex. This observation explains the impurity dependence of the self-deactivation rate constant of water vapor. Analysis of an ultrasonic absorption peak based on the third process yields values for the standard entropy and enthalpy of dissociation of the stably bound H2O dimer.

Zuckerwar, A. J.↗

Determination of the Accomodation Coefficient Using Vapor/Gas Bubble Dynamics in an Acoustic Field

Non-equilibrium liquid/vapor phase transformations can occur in superheated or subcooled liquids in fast processes such as in evaporation in a vacuum, in processing of molten metals, and in vapor explosions. The rate at which such a phase transformation occurs, Xi, can be described by the Hertz-Knudsen-Langmuir formula. More than one century of the history of the accommodation coefficient measurements shows many problems with its determination. This coefficient depends on the temperature, is sensitive to the conditions at the interface, and is influenced by small amounts of impurities. Even recent measurements of the accommodation coefficient for water (Hagen et al, 1989) showed a huge variation in Beta from 1 for 1 micron droplets to 0.006 for 15 micron droplets. Moreover, existing measurement techniques for the accommodation coefficient are complex and expensive. Thus development of a relatively inexpensive and reliable technique for measurement of the accommodation coefficient for a wide range of substances and temperatures is of great practical importance.

Gumerov, Nail A.↗

Synthesis routes to eliminate oxide impurity segregation and their influence on intergrain connectivity in K-doped BaFe 2 As 2 polycrystalline bulks

The poor reproducibility of intergrain critical current density $J_c$ in Fe-based superconductors is often believed to result from uncontrolled grain boundary (GB) connectivity degraded by extrinsic factors such as the local or global impurity concentration or GB porosity or cracks. Earlier we found that Ba and K can appear as oxide impurities at GBs, along with GB-wetting FeAs. In this study, we evaluated how the sample preparation environment and purity of the starting materials influence the polycrystalline $J_c$ in K-doped BaFe 2 As 2 (Ba122) bulks. Using a high-performance glovebox, the oxygen and water levels were significantly reduced, eliminating traces of FeAs. We report oxide impurities and Ba (or K) segregation associated with oxygen in the starting materials were significantly reduced by using high purity starting materials. This combination essentially doubled the best $J_c$(4.2 K) values to 2.3 × 10 5 at self-field and 1.6 × 10 4 A cm –2 at 10 T and analytical scanning transmission electron microscopy showed no GB or O segregation in the best samples, but did show dark Z-contrast and distinct nanoscale porosity. Our work shows that an inert synthesis environment and high purity K and Ba do reduce current-blocking oxygen impurity and GB impurity phases, allowing deeper exploration of the role of extrinsic and intrinsic GB blocking effects in controlling the $J_c$ of polycrystalline Ba122.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Water Contaminant Mitigation in Ionic Liquid Propellant

Appropriate system and operational requirements are needed in order to ensure mission success without unnecessary cost. Purity requirements applied to thruster propellants may flow down to materials and operations as well as the propellant preparation itself. Colloid electrospray thrusters function by applying a large potential to a room temperature liquid propellant (such as an ionic liquid), inducing formation of a Taylor cone. Ions and droplets are ejected from the Taylor cone and accelerated through a strong electric field. Electrospray thrusters are highly efficient, precise, scaleable, and demonstrate low thrust noise. Ionic liquid propellants have excellent properties for use as electrospray propellants, but can be hampered by impurities, owing to their solvent capabilities. Of foremost concern is the water content, which can result from exposure to atmosphere. Even hydrophobic ionic liquids have been shown to absorb water from the air. In order to mitigate the risks of bubble formation in feed systems caused by water content of the ionic liquid propellant, physical properties of the ionic liquid EMI-Im are analyzed. The effects of surface tension, material wetting, physisorption, and geometric details of the flow manifold and electrospray emitters are explored. Results are compared to laboratory test data.

Conroy, David↗

A hybrid regenerative water recovery system for lunar/Mars life support applications

Long-duration manned space missions will require integrated biological and physicochemical processes for recovery of resources from wastes. This paper discusses a hybrid regenerative biological and physicochemical water recovery system designed and built at NASA's Crew and Thermal Systems Division at Johnson Space Center. The system is sized for a four-person crew and consists of a two-stage, aerobic, trickling filter bioreactor; a reverse osmosis system; and a photocatalytic oxidation system. The system was designed to accommodate high organic and inorganic loadings and a low hydraulic loading. The bioreactor was designed to oxidize organics to carbon dioxide and water; the reverse osmosis system reduces inorganic content to potable quality; and the photocatalytic oxidation unit removes residual organic impurities (part per million range) and provides in situ disinfection. The design and performance of the hybrid system for producing potable/hygiene water is described. Aspects of the system such as closure, automation and integration are discussed and preliminary results presented.

Verostko, Charles E.↗