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At least 667 records · Page 37

25 years of environmental remediation in the general separations area of the Savannah river site: lessons learned about what worked and what did not work in soil and groundwater cleanup - 15270

The Savannah River Site, which is owned and administered by the US Department of Energy, covers approximately 900 square kilometers. The General Separation Area is located in the center of the site and includes: radioactive material chemical separations facilities, radioactive waste tank farms, radioactive seepage basins, and the radioactive waste burial grounds. Radioactive wastes were disposed in the General Separation Area from the mid-1950's through the mid-1990's. Operations at the F Canyon began in 1954 and at H Canyon began in 1955. Waste water disposition to the F and H Seepage Basins began soon after operations started in the canyons. The Old Radioactive Waste Burial Ground began operations in 1952 to manage solid waste that could be radioactive from all the site operations, and ceased receiving waste in 1972. The Mixed Waste Management Facility and Low Level Radioactive Waste Disposal Facility received radioactive solid waste from 1969 until 1995. Environmental legislation enacted in the 1970's through 1990's led to changes in waste management and environmental cleanup practices. The US Congress passed the Clean Air Act in 1970 and the Clean Water Act in 1972; the Resource Conservation and Recovery Act was enacted in 1976; the Comprehensive Environmental Response Compensation, and Liability Act was enacted by Congress in 1980; and the Federal Facilities Compliance Act was signed into law in 1992. Environmental remediation at the Savannah River Site essentially began with a 1987 Settlement Agreement between the Savannah River Site and the State of South Carolina. The site manages several of the larger groundwater remedial activities under the Resource Conservation and Recovery Act for facilities recognized early on as environmental problems. All subsequent remediation projects are managed under a tri-party agreement (Department of Energy, Environmental Protection Agency, and South Carolina Department of Health and Environmental Control) through the Federal Facilities Agreement. Environmental remediation activities during the past 25 years have stabilized and capped seepage basins as well as consolidated and capped waste units and burial grounds in the General Separation Area. Groundwater activities include: pump and treat systems in the groundwater, installation of deep subsurface barrier systems to manage groundwater flow, in situ chemical treatments in the groundwater, and captured contaminated groundwater discharges at the surface for management in a forest irrigation system. Concentrations of contaminants in the aquifers beneath the General Separation Area and in surface water streams in the General Separation Area have decreased over the past 25 years. Closure of 65 waste sites and 4 Resource Conservation and Recovery Act facilities has been successfully accomplished. Environmental clean-up has progressed to the stage where most of the work involves monitoring, optimization, and maintenance of existing remedial systems. Many lessons have been learned in the process of remediating the General Separations Area. Geo-textile covers outperform low permeability clay caps, especially with respect to the amount of repairs required to upkeep the drainage layers as the caps age. Passive and enhanced natural processes to address contamination are much more cost effective than pump and treat systems. Forest irrigation can be very effective in water management situations with non-accumulative contaminants such as tritium and volatile organic contaminants. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Condensed Phase Deactivation of Solid Brønsted Acids in the Dehydration of Fructose to Hydroxymethylfurfural

Catalyst deactivation resulting from the hydrothermal leaching of sulfonic acid residues and the deposition of carbonaceous residues was studied using condensed phase flow reactor experiments along with state-of-the-art solid-state NMR. Several commercially available sulfonic acid-containing heterogeneous Brønsted acids were compared by measuring the rates of sulfonic acid breakdown at hydrothermal flow conditions of 160 °C. Amberlyst 45 was found to show higher hydrothermal stability when compared to both Nafion and Amberlyst 15, with <10% loss in acidity after 48 h. The dehydration reaction of fructose to hydroxymethylfurfural (HMF) was used as a model system to compare deactivation rates from carbon deposition (fouling) to those from sulfur leaching, and deactivation from fouling was shown to be dramatically faster than that from sulfonic acid leaching alone. Fouling rates were then investigated in greater detail by comparing the influence of several factors including reactant, solvent, residence time, and feed concentration. The only successful approach to minimize fouling was the use of a polar aprotic solvent [dimethyl sulfoxide (DMSO)] with dilute (50 mM) reactant streams. In aqueous systems, operating the reactor in a regime with low conversion conditions (short residence times) does not significantly improve the longevity of the catalyst. Spent catalysts were characterized using 13C solid-state NMR spectroscopy enhanced by dynamic nuclear polarization. Additionally, in situ 1H and 13C high-resolution magic angle spinning (HR-MAS) solid-state NMR spectroscopies were used to investigate the solvent influence at the catalyst interface. The HR-MAS NMR studies showed that in polar aprotic solvents, the increased acidity leads to greater selectivity toward HMF; more importantly, that the dehydration products do not readily adhere to the surface in DMSO, in contrast to their behavior in water. The results demonstrate that more active and longer-lived acid catalysts could be obtained by tuning the solvent and surface polarity to allow for efficient desorption of products, thereby reducing the catalyst deactivation that occurs due to fouling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Preparative electrophoresis for space

A premise of continuous flow electrophoresis is that removal of buoyancy-induced thermal convection caused by axial and lateral temperature gradients results in ideal performance of these instruments in space. Although these gravity dependent phenomena disturb the rectilinear flow in the separation chamber when high voltage gradients or thick chambers are used, distortion of the injected sample stream due to electrohydrodynamic effects cause major broadening of the separated bands. The electrophoresis separation process is simple, however flow local to the sample filament produced by the applied electric field have not been considered. These electrohydrodynamic flows distort the sample stream and limit the separation. Also, electroosmosis and viscous flow combine to further distort the process. A moving wall concept is being proposed for space which will eliminate and control the disturbances. The moving wall entrains the fluid to move as a rigid body and produces a constant residence time for all samples distributed across the chamber thickness. The moving wall electrophoresis chamber can only be operated in space because there is no viscous flow in the chamber to stabilize against thermal convection.

Rhodes, Percy H.↗

Preparative electrophoresis for space

A premise of continuous flow electrophoresis is that removal of buoyance-induced thermal convection caused by axial and lateral temperature gradients results in ideal performance of these instruments in space. Although these gravity dependent phenomena disturb the rectilinear flow in the separation chamber when high voltage gradients or thick chamber are used, distortion of the injected sample stream due to electrodynamic effects cause major broadening of the separated bands. The electrophoresis separation process is simple, however flow local to the sample filament produced by the applied electric field were not considered. These electrohydrodynamic flows distort the sample stream and limit the separation. Also, electroosmosis and viscous flow combine to further distort the process. A moving wall concept is being proposed for space which will eliminate and control the disturbances. The moving wall entrains the fluid to move as a rigid body and produces a constant residence time for all samples distributed across the chamber thickness. The moving wall electrophoresis chamber can only be operated in space because there is no viscous flow in the chamber to stabilize against thermal convection.

Rhodes, Percy H.↗

Take-Off and Landing Characteristics of a 0.13-Scale Model of the Convair XFY-1 Vertically Rising Airplane in Steady Winds, TED No. NACA DE 368

An experimental investigation has been conducted to determine the stability and control characteristics of a 0.13-scale free-flight model of the Convair XFY-1 airplane during take-offs and landings in steady winds. The tests indicated that take-offs in headwinds up to at least 20 knots (full scale) will be fairly easy to perform although the airplane may be blown downstream as much as 3 spans before a trim condition can be established. The distance that the airplane will be blown down-stream can be reduced by restraining the upwind landing gear until the instant of take-off. The tests also indicated that spot landings in headwinds up to at least 30 knots (full scale) and in crosswinds up to at least 20 knots (full scale) can be accomplished with reasonable accuracy although, during the landing approach, there will probably be an undesirable nosing-up tendency caused by ground effect and by the change in angle of attack resulting from vertical descent. Some form of arresting gear will probably be required to prevent the airplane from rolling downwind or tipping over after contact. This rolling and tipping can be prevented by a snubbing line attached to the tip of the upwind' wing or tail or by an arresting gear consisting of a wire mesh on the ground and hooks on the landing gear to engage the mesh.

Schade, Robert O.↗

CO.sub.2 removal sorbent composition with high chemical stability during multiple cycles

Disclosed herein is a clay-alkali-amine CO.sub.2 sorbent composition prepared by integrating a clay substrate, basic alkali salt, and amine liquid. The basic alkali salt is present relative to the clay substrate in a weight ratio of from about 1 part to about 50 parts per 100 parts of the clay substrate. The amine liquid is present relative to a clay-alkali combination in a weight ratio of from about 1 part to about 10 parts per 10 parts of the clay-alkali combination. The clay-alkali-amine C02 sorbent is particularly advantageous for low temperature CO.sub.2 removal cycles in a gas stream having a C02 concentration less than around 2000 ppm and an oxygen concentration around 21%, such as air.

54 ENVIRONMENTAL SCIENCES↗

Effects of Synthesis Gas Concentration, Composition, and Operational Time on Tubular Solid Oxide Fuel Cell Performance

There is tremendous potential to utilize the exhaust gases and heat already present within combustion chambers to generate electrical power via solid oxide fuel cells (SOFCs). Variations in system design have been investigated as well as thorough examinations into the impacts of environmental conditions and fuel composition/concentration on SOFC performance. In an attempt to isolate the impacts of carbon monoxide and hydrogen concentration ratios within the exhaust stream, this work utilizes multi-temperature performance analyses with simulated methane combustion exhaust as fuel combined with dilute hydrogen baseline tests. These comparisons reveal the impacts of the complex reaction pathways carbon monoxide participates in when used as an SOFC fuel. Despite these complexities, performance reductions as a result of the presence of carbon monoxide are low when compared to similarly dilute hydrogen as a fuel. This provides further motivation for the continued development of SOFC-CHP systems. Stability testing performed over 80 h reveals the need for careful control of the operating environment as well as signs of carbon deposition. As a result of gas flow disruption, impacts of anode oxidation that may normally not hinder power production become significant factors in addition to coarsening of the anode material. Thermal management and strategies to minimize these impacts are a topic of future research.

54 ENVIRONMENTAL SCIENCES↗

Radium/Barium Waste Project

The treatment, shipping, and disposal of a highly radioactive radium/barium waste stream have presented a complex set of challenges requiring several years of effort. The project illustrates the difficulty and high cost of managing even small quantities of highly radioactive Resource Conservation and Recovery Act (RCRA)-regulated waste. Pacific Northwest National Laboratory (PNNL) research activities produced a Type B quantity of radium chloride low-level mixed waste (LLMW) in a number of small vials in a facility hot cell. The resulting waste management project involved a mock-up RCRA stabilization treatment, a failed in-cell treatment, a second, alternative RCRA treatment approach, coordinated regulatory variances and authorizations, alternative transportation authorizations, additional disposal facility approvals, and a final radiological stabilization process.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Radium/Barium waste project - 15043

The treatment, shipping, and disposal of a highly radioactive radium/barium waste stream have presented a complex set of challenges requiring several years of effort. The project illustrates the difficulty and high cost of managing even small quantities of highly radioactive Resource Conservation and Recovery Act (RCRA)-regulated waste. Pacific Northwest National Laboratory (PNNL) research activities produced a Type B quantity of radium chloride low-level mixed waste (LLMW) in a number of small vials in a facility hot cell. The resulting waste management project involved a mock-up RCRA stabilization treatment, a failed in-cell treatment, a second, alternative RCRA treatment approach, coordinated regulatory variances and authorizations, alternative transportation authorizations, additional disposal facility approvals, and a final radiological stabilization process. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Time-Temperature-Transformation (TTT) Diagram for a Sludge Batch 9 Glass Composition Based on Coupled-Operation with the Salt Waste Processing Facility

The amorphous structure of a glass waste form has the potential to rearrange into crystalline phases at temperatures between the liquidus temperature and the glass transition temperature (Tg). Certain phases that can form will be detrimental to the durability of the glass and it is important to know the conditions that promote devitrification. The canister-centerline-cooling (CCC) profile is used to replicate the area within the center of the Defense Waste Processing Facility (DWPF) canister with the slowest cooling during the initial cool down after pouring, which has the greatest potential for crystallization. Other time-temperature conditions that cause significant changes in either phase structure or phase composition are identified by a time-temperature-transformation (TTT) study. The phase stability of a waste form must be determined as a part of the Waste Acceptance Product Specifications (WAPS) if it is to eventually be stored in a geologic repository. This requires the creation of a TTT diagram and analysis of the Tg, as defined by the Department of Energy (DOE). The previous TTT study for a DWPF glass waste form was completed in 2010 prior to coupled operation with the Salt Waste Processing Facility (SWPF). SWPF transfers two high activity waste streams to DWPF for vitrification: a cesium-containing strip effluent and a stream containing monosodium titanate/sludge solids. These SWPF streams were first transferred to DWPF for vitrification during Sludge Batch 9 (SB9) in 2021. The impact of these SWPF streams on crystallization behavior was not determined in previous studies and the need for data to satisfy WAPS Specification 1.4 for SB9 was identified.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Additional support for the TDK/MABL computer program

An advanced version of the Two-Dimensional Kinetics (TDK) computer program was developed under contract and released to the propulsion community in early 1989. Exposure of the code to this community indicated a need for improvements in certain areas. In particular, the TDK code needed to be adapted to the special requirements imposed by the Space Transportation Main Engine (STME) development program. This engine utilizes injection of the gas generator exhaust into the primary nozzle by means of a set of slots. The subsequent mixing of this secondary stream with the primary stream with finite rate chemical reaction can have a major impact on the engine performance and the thermal protection of the nozzle wall. In attempting to calculate this reacting boundary layer problem, the Mass Addition Boundary Layer (MABL) module of TDK was found to be deficient in several respects. For example, when finite rate chemistry was used to determine gas properties, (MABL-K option) the program run times became excessive because extremely small step sizes were required to maintain numerical stability. A robust solution algorithm was required so that the MABL-K option could be viable as a rocket propulsion industry design tool. Solving this problem was a primary goal of the phase 1 work effort.

Nickerson, G. R.↗

Electrochemical Detection of Multiple Bioprocess Analytes

An apparatus that includes highly miniaturized thin-film electrochemical sensor array has been demonstrated as a prototype of instruments for simultaneous detection of multiple substances of interest (analytes) and measurement of acidity or alkalinity in bioprocess streams. Measurements of pH and of concentrations of nutrients and wastes in cell-culture media, made by use of these instruments, are to be used as feedback for optimizing the growth of cells or the production of desired substances by the cultured cells. The apparatus is designed to utilize samples of minimal volume so as to minimize any perturbation of monitored processes. The apparatus can function in a potentiometric mode (for measuring pH), an amperometric mode (detecting analytes via oxidation/reduction reactions), or both. The sensor array is planar and includes multiple thin-film microelectrodes covered with hydrous iridium oxide. The oxide layer on each electrode serves as both a protective and electrochemical transducing layer. In its transducing role, the oxide provides electrical conductivity for amperometric measurement or pH response for potentiometric measurement. The oxide on an electrode can also serve as a matrix for one or more enzymes that render the electrode sensitive to a specific analyte. In addition to transducing electrodes, the array includes electrodes for potential control. The array can be fabricated by techniques familiar to the microelectronics industry. The sensor array is housed in a thin-film liquid-flow cell that has a total volume of about 100 mL. The flow cell is connected to a computer-controlled subsystem that periodically draws samples from the bioprocess stream to be monitored. Before entering the cell, each 100-mL sample is subjected to tangential-flow filtration to remove particles. In the present version of the apparatus, the electrodes are operated under control by a potentiostat and are used to simultaneously measure the pH and the concentration of glucose. It is anticipated that development of procedures for trapping more enzymes into hydrous iridium oxide (and possibly into other electroactive metal oxides) and of means for imparting long-term stability to the transducer layers should make it possible to monitor concentrations of products of many enzyme reactions for example, such key bioprocess analytes as amino acids, vitamins, lactose, and acetate.

Rauh, R. David↗

Technical Note: Spot characteristic stability for proton pencil beam scanning

Purpose: The spot characteristics for proton pencil beam scanning (PBS) were measured and analyzed over a 16 month period, which included one major site configuration update and six cyclotron interventions. The results provide a reference to establish the quality assurance (QA) frequency and tolerance for proton pencil beam scanning. Methods: A simple treatment plan was generated to produce an asymmetric 9-spot pattern distributed throughout a field of 16 × 18 cm for each of 18 proton energies (100.0–226.0 MeV). The delivered fluence distribution in air was measured using a phosphor screen based CCD camera at three planes perpendicular to the beam line axis (x-ray imaging isocenter and up/down stream 15.0 cm). The measured fluence distributions for each energy were analyzed using in-house programs which calculated the spot sizes and positional deviations of the Gaussian shaped spots. Results: Compared to the spot characteristic data installed into the treatment planning system, the 16-month averaged deviations of the measured spot sizes at the isocenter plane were 2.30% and 1.38% in the IEC gantry x and y directions, respectively. The maximum deviation was 12.87% while the minimum deviation was 0.003%, both at the upstream plane. After the collinearity of the proton and x-ray imaging system isocenters was optimized, the positional deviations of the spots were all within 1.5 mm for all three planes. During the site configuration update, spot positions were found to deviate by 6 mm until the tuning parameters file was properly restored. Conclusions: For this beam delivery system, it is recommended to perform a spot size and position check at least monthly and any time after a database update or cyclotron intervention occurs. A spot size deviation tolerance of <15% can be easily met with this delivery system. Deviations of spot positions were <2 mm at any plane up/down stream 15 cm from the isocenter.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Response of Stream Metabolism to Coarse Woody Debris Additions Along a Catchment Disturbance Gradient

We evaluated the ecological effectiveness of an in-stream restoration project involving coarse woody debris (CWD) additions to streams along an upland soil and vegetation disturbance gradient at the Fort Benning Military Installation near Columbus, GA. We examined short-term (immediate effectiveness) and longer-term (sustainability) responses to CWD additions by measuring ecosystem metabolism rates in 8 streams quarterly over a 6-year period, including 3 years before (2001–2003) and 3 years after (2004–2006) CWD additions that were made to half of the streams. Ecosystem respiration (ER) rates in most CWD addition streams increased relative to control streams from spring 2004 through autumn 2005, suggesting heterotrophic bacteria were the initial responders to CWD additions. Gross primary production (GPP) rates remained low (typically < 0.3 g O 2 m -2 d -1 ) but increased in some CWD addition streams relative to control streams in spring 2004 and 2005. The magnitude of ER increases in CWD addition streams during the first two years post-addition increased with catchment disturbance intensity, indicating that more heavily disturbed streams responded most strongly to restorations—an important consideration when targeting future restoration locations. Because restorations did not address actual upland disturbance, continued high erosion rates resulted in 32–77% of the added CWD being buried by year two and a corresponding return of GPP and ER rates to pre-CWD addition levels by year three. If restoration projects do not adequately address the source of catchment disturbances, CWD additions will provide only short-term increases in streambed structure and stability, hydrodynamic complexity, and nutrient and organic matter processing and retention.

54 ENVIRONMENTAL SCIENCES↗

A Bimetallic Nickel–Gallium Complex Catalyzes CO 2 Hydrogenation via the Intermediacy of an Anionic d 10 Nickel Hydride

Large-scale CO2 hydrogenation could offer a renewable stream of industrially important C1 chemicals while reducing CO2 emissions. Critical to this opportunity is the requirement for inexpensive catalysts based on earth-abundant metals instead of precious metals. We report a nickel-gallium complex featuring a Ni(0)→Ga(III) bond that shows remarkable catalytic activity for hydrogenating CO2 to formate at ambient temperature (3150 turnovers, turnover frequency = 9700 h-1), compared with prior homogeneous Ni-centred catalysts. The Lewis acidic Ga(III) ion plays a pivotal role by stabilizing reactive catalytic intermediates, including a rare anionic d10 Ni hydride. The structure of this reactive intermediate shows a terminal Ni-H, for which the hydride donor strength rivals those of precious metal-hydrides. Collectively, our experimental and computational results demonstrate that modulating a transition metal center via a direct interaction with a Lewis acidic support can be a powerful strategy for promoting new reactivity paradigms in base-metal catalysis. The work was supported as part of the Inorganometallic Catalysis Design Center, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences under Award DE-SC0012702. R.C.C. and M.V.V. were supported by DOE Office of Science Graduate Student Research and National Science Foundation Graduate Research Fellowship programs, respectively. J.C.L., S.A.B., and A.M.A. were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cell-free bioelectrocatalytic platform for carbon dioxide reduction (Final Technical Report)

The University of Minnesota (UMN) EcoSynBio Team aimed to develop a cell-free, enzyme-based platform for the electro- biocatalytic conversion of CO2 into formate as a platform chemical for further upgrading. This type of bio electrocatalytic process delivers a clean product stream without the need for extensive separation from the electrolyte as in electrochemical synthesis and microbial processes. The reduction reaction is catalyzed by metal-dependent formate dehydrogenases (mFDHs) that are capable of efficient electrocatalytic CO2 reduction without the need of costly co-factors. The development of an efficient, scalable electrobiocatalytic process with high total turnover numbers and viable space time yields, however, was not without its challenges. The UM team has developed a protein-based scaffolding system that facilitates enzyme stabilization and attachment to electrodes along with electron transfer. Yet, although FDHs are highly promising enzymes for cell-free, electrobiochemical CO2 reduction, they are also greatly understudied and especially for applications in electrocatalysis. The UM team used the best described mFDH from Clostridium as its benchmark system and spent significant time and effort in attempting to replicate published data and finally, redesigned a recombinant production system for proper metal co-factor incorporation. The UM team has also identified a small set of new enzyme homologs from extreme microorganisms with superior stabilities that have yielded initial structural data for further engineering. In addition, a new bioelectrocatalytic reactor system has been developed that can be 3D printed and used for enzyme attachment to electrodes. In summary the project has generated critical basic information for the further development of this class of enzymes for the electricity driven reduction of CO2 into formate as platform chemical for upgrading into various other chemicals, including fuels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

AIROscope: Ames infrared balloon-borne telescope

A balloon-borne telescope system designed for astronomical observations at infrared wavelengths is discussed. The telescope is gyro-stabilized with updated pointing information derived from television, star tracker, or ground commands. The television system furnishes both course and fine acquisition after initial orientation using a pair of fluxgate servo compasses. Command and control is by a UHF link with 256 commands available. Scientific and engineering data are telemetered to the ground station via narrow band F.M. in the L band. The ground station displays all scientific, engineering and status information during the flights and records the command and telemetry digital bit stream for detailed analysis. The AIROscope telescope has a 28-inch diameter primary mirror and Dall-Kirkham optics. The beam is modulated by oscillating a secondary mirror at 11 or 25 Hz with provision for left or right beam fixed positions by command.

Koontz, O. L.↗

Control of Supersonic Boundary Layers Using Steady Suction

Control of supersonic boundary layers using steady suction through a series of very small two-dimensional strips is numerically investigated at a free stream Mach number of 1.8. The mean flow induced by rows of suction holes is also computed. Both the steady and unsteady solutions are obtained by solving the full Navier-Stokes equations using the 5th-order accurate weighted essentially non-oscillatory (WENO) scheme for space discretization and using third-order total-variationdiminishing (TVD) Runge-Kutta scheme for time integration. Computations for the two-dimensional cases are performed at suction coefficients 0.001 and 0.002 to investigate the stabilizing effects of suction. The simulation showed that a series of shock waves are generated at the slots. The stability results showed that the total amplification is reduced up to the end of the computational domain. However, the growth rates become larger at downstream distances away from the suction region. The computations for the suction holes showed the generation of Mach waves from each hole and the formation of longitudinal vortices.

Balakumar, P.↗