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'Treatment of High Level Waste (HLW) is the second most costly problem identified by OEM. In order to minimize costs of disposal, the volume of HLW requiring vitrification and long term storage must be reduced. Methods for efficient separation of chromium from waste sludges, such as the Hanford Tank Wastes (HTW), are key to achieving this goal since the allowed level of chromium in high level glass controls waste loading. At concentrations above 0.5 to 1.0 wt.% chromium prevents proper vitrification of the waste. Chromium in sludges most likely exists as extremely insoluble oxides and minerals, with chromium in the plus III oxidation state [1]. In order to solubilize and separate it from other sludge components, Cr(III) must be oxidized to the more soluble Cr(VI) state. Efficient separation of chromium from HLW could produce an estimated savings of $3.4B[2]. Additionally, the efficient separation of technetium [3], TRU, and other metals may require the reformulation of solids to free trapped species as well as the destruction of organic complexants. New chemical processes are needed to separate chromium and other metals from tank wastes. Ideally they should not utilize additional reagents which would increase waste volume or require subsequent removal. The goal …

'The long-term goal of this research is to manipulate single-gene traits into plants, enabling them to process heavy metals and remediate heavy-metal pollution by resistance, sequestration, removal, and management of these contaminants (Meagher and Rugh, 1996; Meagher et al., 1997). The working hypothesis behind this proposal was that transgenic plants expressing both the bacterial organo mercury lyase (merB) and the mercuric ion reductase gene (merA) will (A) remove the mercury from polluted sites and (B) prevent methyl mercury from entering the food chain. The authors have had a very successful first year either testing aspects of this hypothesis directly or preparing material needed for future experiments. The results are outlined below under goals A and B, which are explicit in this hypothesis. There were less than 10% of the funds remaining in any category as projected in the first 12 month budget at the end of the first year, with the exception of the equipment category which had 25% of the funds remaining ({approximately} $8,000). Much of this remaining equipment money is being spent this week on a mercury vapor analyzer. It might be useful to remember that at the time this grant was awarded, the authors had successfully engineered …

A systematic test of various characteristics, such as gain, dark current, maximum peak current, stability and relative quantum efficiency, has been made to evaluate about 2,000 photomultiplier tubes for the upgraded CDF Endplug calorimeters. The phototubes are Hamamatsu R4125,19mm diameter with green-extended photocathode. In this report we discuss the distribution of the major characteristics measured and the failure mode. Comparisons between independent measurements made on some of the characteristics are used to evaluate the quality of the measurement itself.

The authors present experimental measurements of the accessible pore fraction in ceramic matrix composites during consolidation by vapor phase infiltration. For two topologically distinct filament architectures, the accessible pore fraction decreased during consolidation with a power law decay and a critical scaling exponent of 0.41 (R{sup 2} = 0.97). A three-dimensional analysis of the percolating pores revealed that the structures became topologically equivalent and simply connected near the critical density.

'The specific aim of this report is to parameterize force field to reproduce geometries and relative energetics of metal-ligand complexes for cesium, strontium, plutonium, uranium, americium and other relevent alkali, transition, lanthanide and actinide metals. As an initial attempt to examine parametrization, Dr. Yasuo Takeuchi has examined parameters for iron in combination with the molecular mechanics force field. The authors realize that most of the current ad hoc methodogies used to model metal interactions in the past do not have a firm theoretical foundation for modeling the d and f orbitals. They have, therefore, started a collaboration with Prof. Anders Carlsson of the Department of Physics to provide a theoretically correct functional form for the metal force field. Prof. Carlsson has an extensive track record in the derivation of the form of angular force fields from analysis of the quantum-mechanical electronic structure. His most important related works have treated the angular forces around transition-metal (TM) atoms in an aluminum host, the angular forces in elemental bcc transition metals, and the origins of angular and torsional forces in well-bonded s-p systems. They propose to apply the basic ideas of these calculations to developing force laws for transition metal ions in biomolecules. …

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'During FY97 this study has developed unique accelerator mass spectrometry (AMS) analytical techniques for measurement of {sup 99}Tc and {sup 129}I, which compliments an improved capability for measurement of {sup 36}Cl. The ability to measure these nuclides in natural soil samples has been demonstrated through analytical results obtained during FY97. Methods to determine the distribution of these nuclides in their natural setting, which will vary depending on site-specific chemical conditions, have also been developed. Spatially well-characterized soil samples have been collected from the vadose zone to a depth of -5 meters at the Nevada Test Site. To do this, a deep trench has been excavated and the geological setting for the soils has been well documented. Physical, chemical, and isotopic analysis of these soil samples during the course of this research project will result in a numerical computer model for moisture and radionuclide migration in arid soils that is valuable to nuclear waste storage, site remediation, and groundwater recharge concerns.'

'There are enormous amounts of heavy metals in the environment, much of it in the form of organometallic compounds resulting from various types of industrial and military waste. Nearly all of these metals and compounds are highly toxic to biological organisms including humans. However, some bacteria thrive in the presence of high concentrations of heavy metal toxins because they possess efficient mechanisms for the detoxification of these metals and compounds. Heavy metals appear to be universally toxic because of their non-selective chemistry, for example Hg(II) reacts with essentially all exposed sulfhydryl groups on proteins, thus, it may seem surprising that any organism at all can survive these chemical insults much less those that grow in a toxic milieu. However, the prebiotic environment was undoubtedly heavily polluted with heavy metals from geological processes, and the most primitive organisms simply had to evolve mechanisms for dealing with them if they were going to be able to utilize Cys, His, and the other amino acids that contribute to metal binding sites in their proteins. Genes associated with bacterial resistance to Ag, AsO{sub 2}, AsO{sub 4}, Bi, Cd, Co, CrO{sub 4}, Cu, Hg, iNi, TeO{sub 3}, TI, Pb, Zn, and other metals of environmental …

'This research is aimed at improving methods for characterizing underground contamination sites and for monitoring how they change with time. Particular emphasis is placed on identifying and quantifying the effects of intrinsic remediation and verifying the efficacy of engineered remediation activities. Isotopic measurements of elements such as C, O, H, He, Cl, and Sr, which are present in groundwater and soil gas, provide a quantitative measure of material balance. They can be used to identify the sites of origin of contaminants in groundwater, and to determine if contaminants are being destroyed as a result of natural processes or engineered processes. Isotope ratios also can be used to trace the migration of fluids that underground contaminants, such as steam and chemical reactions are occurring underground destruction of TCE usually produces carbon dissolution of calcite. are pumped down wells to destroy or confine grout, and they can be utilized to diagnose what and what materials are reacting. For example, dioxide, but carbon dioxide can also come from There are many isotopic ratios that can be measured in groundwater and vadose zone gas that could be valuable for characterizing remediation sites and monitoring remediation activities; The authors concentrate on a few that are …

'Metabolism of Chlorinated Hydrocarbons Laboratory and field tests with poplar in tissue culture, bioreactors, and field sites have shown that, unlike bacteria, these plants are able to carry out complete degradation of fully chlorinated alkanes and alkenes to carbon dioxide and chloride. Carbon dioxide was produced as a product of the degradation of trichloroethylene (TCE), carbon tetrachloride (CT), and perchloroethylene (PCE) when axenic tissue cultures of poplar cells were exposed to radiolabelled compounds. The apparent degradation of PCE and CT, fully chlorinated hydrocarbons, in these aerobic plants is remarkable when contrasted to the lack of comparable aerobic degradation by bacteria. Oxidized metabolites, such as trichloroethanol, and di- and trichloroacetic acid, were detected in cell cultures exposed to TCE, suggesting the involvement of cytochrome P450s or other monooxygenase activities. Mass balance experiments with small poplar plants in laboratory reactors showed that significant TCE and CT was volatilized from the leaves, while a similar fraction of radiolabeled carbon from these chlorinated solvents was retained in the plant tissue.'

'The objective of this project is to develop the scientific basis for characterizing contaminant plumes in the earth''s subsurface using field measurements of induced polarization (IP) effects. The first-year accomplishments are (1) laboratory experiments on fluid-saturated sandstones quantifying the dependence of spectral IP responses on solution chemistry and rock micro-geometry; (2) library research on the current understanding of electromagnetic coupling effects on IP data acquired in the field: and (3) development of prototype forward modeling and inversion algorithms for interpreting IP data in terms of 3-D models of complex resistivity.'

'This project has as its focus the design and synthesis of polyammonium macrocyclic receptors for oxoanions of environmental importance. The basic research aspects of this project involve synthesis (and the search for improved synthetic methods), solid state structure determination and thermodynamics studies (to ascertain structural criteria for and strength of anion binding), and molecular dynamics simulations (to assess solution characteristics of the interactions between anions and their receptors). Applications-oriented goals include the fabrication of more efficient anion-selective electrodes and the use of these compounds in liquid- liquid separations. The latter goal is the subcontract with Bruce Moyer at Oak Ridge National Laboratory. This first year the authors have focused on nitrates and phosphates. Considerable progress has been made in the basic areas of synthesis, solid state Structure, and molecular dynamics. Anion selective electrodes have also be made which show promising selectivities for oxoanions of interest. Below are described the major findings and significance in the categories of synthesis, structure and molecular dynamics, and electrode studies. Synthesis. The synthesis of polyaza macrocycles which are the focus of these studies is often tedious and time-consuming. A major breakthrough which the authors have made this year is to identify other polyaza macrocycles, which …

'The overall objective of this research is to investigate the influence of coupled physical and chemical heterogeneity on the migration and entrapment of DNAPLs in the saturated zone. This research includes laboratory and numerical investigations for a matrix of fluid and solid properties encompassing a range of wettability characteristics. Specific objectives include: (1) quantification of medium wettability and interfacial tensions; (2) determination of hydraulic property relations; (3) two-dimensional infiltration experiments; (4) modification of a continuum based multiphase flow simulator to account for physical heterogeneity, saturation independent and saturation dependent wettability, and concentration dependent wettability and interfacial tension; and (5) utilization of this model to explore the potential influence of coupled physical and chemical heterogeneities on the migration of DNAPLs and the development of innovative remediation schemes. Research conducted during this period was directed primarily towards the accomplishment of goals (1), (2), (4) and (5); specific details are given below. Goal (3) builds upon results from the other objectives and will, therefore, be started in the coming year.'

'The author has made significant progress in developing innovative methods for investigating the mechanism and extent of in situ bioremediation of chlorinated organic solvents. These methods use precise isotopic ratio measurements of chlorine and carbon in reactant and product species in laboratory experiments and in materials from field demonstration sites. Specific tasks completed during FY 1997 include: (1) refinement and publication of a new analytical method for precise determination of chlorine and carbon isotope ratios in chlorinated volatile organic compounds; (2) laboratory experiments involving biological degradation of chlorinated solvents in liquid cultures and soil columns; and (3) use of chlorine and carbon isotope ratios to investigate natural attenuation of trichloroethene at the Paducah Gaseous Diffusion Plant. This work can have immediate impact because it will provide the fundamental basis for a new and cost-effective means of evaluating and monitoring the effectiveness of in situ bioremediation schemes for chlorinated organic solvents in soils, vadose horizons, and groundwater plumes.'

The mathematical models and numerical methods employed by the FEHM application, a finite-element heat- and mass-transfer computer code that can simulate nonisothermal multiphase multi-component flow in porous media, are described. The use of this code is applicable to natural-state studies of geothermal systems and groundwater flow. A primary use of the FEHM application will be to assist in the understanding of flow fields and mass transport in the saturated and unsaturated zones below the proposed Yucca Mountain nuclear waste repository in Nevada. The component models of FEHM are discussed. The first major component, Flow- and Energy-Transport Equations, deals with heat conduction; heat and mass transfer with pressure- and temperature-dependent properties, relative permeabilities and capillary pressures; isothermal air-water transport; and heat and mass transfer with noncondensible gas. The second component, Dual-Porosity and Double-Porosity/Double-Permeability Formulation, is designed for problems dominated by fracture flow. Another component, The Solute-Transport Models, includes both a reactive-transport model that simulates transport of multiple solutes with chemical reaction and a particle-tracking model. Finally, the component, Constitutive Relationships, deals with pressure- and temperature-dependent fluid/air/gas properties, relative permeabilities and capillary pressures, stress dependencies, and reactive and sorbing solutes. Each of these components is discussed in detail, including purpose, assumptions and …

An asymmetric muon-proton collider is proposed as an instrument for possible quark structure search. Energy of proton beam is supposed to be some 5-6 times of muon energy. Estimated luminosity of the collider with two rings--the Tevatron accelerator and {mu}-ring--is found to be of the order of 10{sup 33} s{sup -1} cm{sup -2}.

The objective of this project is to develop a comprehensive, interdisciplinary, and quantitative characterization of a fluvial-deltaic reser v oir which will allow realistic inter-well and reservoir-scale modeling to be constructed for improved oil-field development in similiar reservoirs world-wide. The geological and petrophysical properties of the Cretaceous Ferron Sandstone in east-central Utah will be quantitatively determined . Both new and existing data will be integrated into a three-dimensional representation of spatial variations in porosity, storativity, and tensorial rock permeability at a scale appropriate for inter-well to regional-scale reservoir simulation. Results could improve reservoir management through proper infill and extension drilling strategies, reduction of economic risks, increased recovery from existing oil fields, and more reliable reserve calculations . Transfer of the project results to the petroleum industry is an integral component of the project. Four activities continued this quarter as part of the geological and petrophysical characterization of the fluvial-deltaic Ferron Sandstone in the Ivie Creek case-study area: (1) geostatistics, (2) field description of clinoform bounding surfaces, (3) reservoir modeling, and (4) technology transfer.

The overall objective of this project was to learn more about controlling emissions of hazardous air pollutants (HAPs) from coal-fired power plants that are equipped with wet flue gas desulfurization (FGD) systems. The project was included by FETC as a Phase I project in its Mega-PRDA program. Phase I of this project focused on three research areas. These areas in order of priority were: (1) Catalytic oxidation of vapor-phase elemental mercury; (2) Enhanced particulate-phase HAPs removal by electrostatic charging of liquid droplets; and (3) Enhanced mercury removal by addition of additives to FGD process liquor. Mercury can exist in two forms in utility flue gas--as elemental mercury and as oxidized mercury (predominant form believed to be HgCl{sub 2}). Previous test results have shown that wet scrubbers effectively remove the oxidized mercury from the gas but are ineffective in removing elemental mercury. Recent improvements in mercury speciation techniques confirm this finding. Catalytic oxidation of vapor-phase elemental mercury is of interest in cases where a wet scrubber exists or is planned for SO{sub 2} control. If a low-cost process could be developed to oxidize all of the elemental mercury in the flue gas, then the maximum achievable mercury removal across the existing …

The objective of this project to develop an advanced flue gas desulfurization (FGD) process that has decreased capital and operating costs, higher SO{sub 2} removal efficiency, and better by-product solids quality than existing, commercially available technology. A clear liquor process (which uses a scrubbing liquid with no solids) will be used to accomplish this objective rather than a slurry liquor process (which contains solids). This clear liquor scrubbing (CLS) project is focused on three research areas: (1) Development of a clear liquor scrubbing process that uses a clear solution to remove SO{sub 2} from flue gas and can be operated under inhibited-oxidation conditions; (2) Development of an anhydrite process that converts precipitated calcium sulfite to anhydrous calcium sulfate (anhydrite); and (3) Development of an alkali/humidification process to remove HCl from flue gas upstream of the FGD system. The anhydrite process also can be retrofit into existing FGD systems to produce a valuable by-product as an alternative to gypsum. This fits well into another of FETC's PRDA objectives of developing an advanced byproduct recovery subsystem capable of transforming SO{sub 2} into a useable byproduct or high-volume valuable commodities of interest. This paper describes the proposed processes, outlines the test approach, and …

'Biofiltration systems can be used to treat volatile organic compounds (VOCs); however, the systems are poorly understood and are currently operated as black boxes. Common operational problems associated with biofilters include fouling, deactivation, and overgrowth, all of which make biofilters ineffective for continuous, long-term use. The objective of this investigation is to develop generic methods for long-term stable operation, in particular by using selective limitation of supplemental nutrients while maintaining high activity and the ability to regenerate biofilter activity. As part of this effort, the authors will provide a deeper fundamental understanding of the important biological and transport mechanisms in biodestruction of sparingly soluble VOCs and will extend this engineering approach and developed mathematical models to two additional systems of high-priority environmental management (EM) relevance-direct degradation and cometabolic degradation of priority pollutants such as BTEX (benzene, toluene, ethylbenzene, and xylene) and TCE (trichioroethylene), respectively. Preliminary results indicate that the author can control overgrowth of the biofilm while sustaining high degradation rates and develop basic predictive models that elucidate mass transfer and kinetic limitations in this system for alkanes. The alkanes are degraded into CO, and waterwith minimal biomass (due to the methodology proposed). This system will be used to test …

'This research is an integrated physical (geophysical and hydrologic) and microbial study using innovative geophysical imaging and microbial characterization methods to identify key scales of physical heterogeneities that affect the biodynamics of natural subsurface environments. Data from controlled laboratory and in situ experiments at the INEEL Test Area North (TAN) site are being used to determine the dominant physical characteristics (lithologic, structural, and hydrologic) that can be imaged in situ and correlated with microbial properties. Emphasis is being placed on identifying fundamental scales of variation of physical parameters that control transport behavior relative to predicting subsurface microbial dynamics. The outcome will be an improved understanding of the relationship between physical and microbial heterogeneity, thus facilitating the design of bioremediation strategies in similar environments. This work is an extension of basic research on natural heterogeneity first initiated within the DOE/OHER Subsurface Science Program (SSP) and is intended to be one of the building blocks of an integrated and collaborative approach with an INEEL/PNNL effort aimed at understanding the effect of physical heterogeneity on transport properties and biodynamics in natural systems. The work is closely integrated with other EMSP projects at INEEL (Rick Colwell et al.) and PNNL (Fred Brockman and Jim …

'This work is focused on the preparation of novel electrode materials for the degradation of toxic wastes in the DOE complex. One of the goals of this work is to characterize whether it is possible to use controlled doping of TiO{sub 2} with species such as Nb in order to create new electrode materials that will facilitate the destruction of undesirable organics and inorganics, without light and instead only with an applied potential, in the waste tanks at the DOE sites. In the first part of this project, the authors have therefore spent an extensive amount of effort characterizing, as a baseline, the chemical and electrochemical behavior of TiO{sub 2} itself, so that they can make robust comparisons to the behavior of the Nb-doped systems in subsequent work on this project. The preparation of these electrode films is being performed by Marc Anderson at Wisconsin, who is preparing a number of different stoichiometries, grain sizes, etc. for investigation of their electrochemical properties by the Lewis group at Caltech. First they report on the progress of the electrode preparation work, and then they describe progress on the electrochemical work.'