Part 3 (Petroleum System Modeling of the Jurassic Smackover Formation) objectives are to provide an analysis of the Smackover petroleum system in Years 4 and 5 of the project and to transfer effectively the research results to producers through workshops and topical reports. Work Accomplished (Year 5): Task 1 - Basin Flow - Basin flow modeling has been completed and the modeling results are being interpreted for report writing (Table 1). Task 2 - Petroleum Source Rocks - Work on the characterization of Smackover petroleum source rocks has been integrated into the basin flow model. Task 3 - Petroleum Reservoirs - Work on the characterization of Smackover petroleum reservoirs continues. The cores to be described have been identified and many of the cores for the eastern part of the basin have been described. Task 4 - Reservoir Diagenesis - Work on reservoir diagenesis has been initiated. Samples from the cores selected for the reservoir characterization are being used for this task. Work Planned (Year 5): Task 1 - Basin Flow - The report on basin flow will be completed. Task 2 - Petroleum Source Rocks - Petroleum source rock data will be reviewed in light of the basin flow model …

Cool storage technology can be used to significantly reduce energy costs by allowing energy-intensive, electrically driven cooling equipment to be predominantly operated during off peak hours when electricity rates are lower. This Federal Technology Alert, which is sponsored by DOE's Federal Energy Management Program (FEMP), describes the basic types of cool storage technologies and cooling system integration options. In addition, it defines the savings potential in the federal sector, presents application advice, and describes the performance experience of specific federal users. The results of a case study of a GSA building using cool storage technology are also provided.

The objective of the ATS program is to develop ultra-high efficiency, environmentally superior and cost competitive gas turbine systems for base load application in utility, independent power producer and industrial markets. Specific performance targets have been set using natural gas as the primary fuel: {lg_bullet} System efficiency that will exceed 60%(lower heating value basis) on natural gas for large scale utility turbine systems; for industrial applications, systems that will result in a 15% improvement in heat rate compared to currently available gas turbine systems. {lg_bullet} An environmentally superior system that will not require the use of post combustion emissions controls under full load operating conditions. {lg_bullet} Busbar energy costs that are 10% less than current state-of-the-art turbine systems, while meeting the same environmental requirements. {lg_bullet} Fuel-flexible designs that will operate on natural gas but are capable of being adapted to operate on coal-derived or biomass fuels. {lg_bullet} Reliability-Availability-Maintainability (RAM) that is equivalent to the current turbine systems. {lg_bullet} Water consumption minimized to levels consistent with cost and efficiency goals. {lg_bullet} Commercial systems that will enter the market in the year 2000. In Phase I of the ATS program, Siemens Westinghouse found that efficiency significantly increases when the traditional combined-cycle power …

A High Performance Power System (HIPPS) is being developed. This system is a coal-fired, combined cycle plant with indirect heating of gas turbine air. Foster Wheeler Development Corporation and a team consisting of Foster Wheeler Energy Corporation, Bechtel Corporation, University of Tennessee Space Institute and Westinghouse Electric Corporation are developing this system. In Phase 1 of the project, a conceptual design of a commercial plant was developed. Technical and economic analyses indicated that the plant would meet the goals of the project which include a 47 percent efficiency (HHV) and a 10 percent lower cost of electricity than an equivalent size PC plant. The concept uses a pyrolysis process to convert coal into fuel gas and char. The char is fired in a High Temperature Advanced Furnace (HITAF). The HITAF is a pulverized fuel-fired boiler/air heater where steam is generated and gas turbine air is indirectly heated. The fuel gas generated in the pyrolyzer is then used to heat the gas turbine air further before it enters the gas turbine. The project is currently in Phase 2 which includes engineering analysis, laboratory testing and pilot plant testing. Research and development is being done on the HIPPS systems that are not …

This report presents work carried out under contract DE-AC22-95PC95144 ''Engineering Development of Coal-Fired High Performance Systems Phase II and III.'' The goals of the program are to develop a coal-fired high performance power generation system (HIPPS) that is capable of: thermal efficiency (HHV) {ge} 47% NOx, SOx, and particulates {le} 10% NSPS (New Source Performance Standard) coal providing {ge} 65% of heat input all solid wastes benign cost of electricity {le}{le} 90% of present plants Phase I, which began in 1992, focused on the analysis of various configurations of indirectly fired cycles and on technical assessments of alternative plant subsystems and components, including performance requirements, developmental status, design options, complexity and reliability, and capital and operating costs. Phase I also included preliminary R&D and the preparation of designs for HIPPS commercial plants approximately 300 MWe in size. Phase II, had as its initial objective the development of a complete design base for the construction and operation of a HIPPS prototype plant to be constructed in Phase III. As part of a descoping initiative, the Phase III program has been eliminated and work related to the commercial plant design has been ended. The rescoped program retained a program of engineering research …

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This project has been focused on equilibrium and transport properties of gas-liquid, liquid-liquid, and solid-liquid systems under electric fields. The objective was to intensify separations methods that are used or can be used to process liquid waste or contaminated groundwater within DOE sites. Examples of processes that have been investigated are distillation (gas-liquid), extraction (liquid-liquid), and sorption (solid-liquid). Effects of electric fields on phase equilibria and interfacial transport have been investigated. So far, this project was directed at basic research on a broadly crosscutting concept. The results advocate continuation of this research in two directions, with the objective to solve problems related to solvent extraction of tank waste and groundwater treatment.

Laser ablation (LA) with inductively coupled plasma mass spectrometry (ICP-MS) has been demonstrated as a viable technology for sample characterization within the EM complex. Laser ablation systems have been set up at the Hanford Site, Savannah River Plant, the Pu immobilization program (MD), Los Alamos, and at numerous other DOE facilities. Characterization of elemental and isotopic chemical constituents is an important function in support of tank-waste operation and remediation functions. Proper waste characterization enables safe operation of the tank farms, resolution of tank safety questions, and development of processes and equipment for retrieval, pretreatment, and immobilization of tank waste. All of these operations are dependent on the chemical analysis of tank waste (1). A specified need by the Tanks Focus Area (TFA) is to validate the laser ablation mass spectrometer (LA/MS) technology through round robin testing of standard materials and through fundamental studies of the laser ablation process (2). Advancement of the laser ablation technology is warranted to guarantee accuracy of analysis for the diversity of complex EM samples. This EMSP research endeavored to understand fundamental laser-ablation and ICP-MS detection characteristics, to ensure accurate and sensitive analytical characterization for EM wastesite samples. The difficulty in characterization of EM waste samples …

Gas injection in oil reservoirs offers huge potential for improved oil recovery. However, successful design of a gas injection process requires a detailed understanding of a variety of different significant processes, including the phase behavior of multicomponent mixtures and the approach to multi-contact miscibility in the reservoir, the flow of oil, water and gas underground, and the interaction of phase behavior reservoir heterogeneity and gravity on overall performance at the field scale. This project attempts to tackle all these issues using a combination of theoretical, numerical and laboratory studies of gas injection. The aim of this work is to develop a set of ultra-fast compositional simulation tools that can be used to make field-scale predictions of the performance of gas injection processes. To achieve the necessary accuracy, these tools must satisfy the fundamental physics and chemistry of the displacement from the pore to the reservoir scales. Thus this project focuses on four main research areas: (1) determination of the most appropriate methods of mapping multicomponent solutions to streamlines and streamtubes in 3D; (2) development of techniques for automatic generation of analytical solutions for one-dimensional flow along a streamline; (3) experimental investigations to improve the representation of physical mechanisms that govern …

The purpose of this study is to determine the bioavailability of organic solvents following dermal exposures to contaminated soil and water. Breath analysis is being used to obtain real-time measurements of volatile organics in expired air following exposure in rats and humans. Rhesus monkeys were used as surrogates for humans in benzene exposures. The exhaled breath data was analyzed using physiologically based pharmacokinetic (PBPK) models to determine the dermal bioavailability of organic solvents under realistic exposure conditions. The end product of this research will be a tested framework for the rapid screening of real and potential exposures while simultaneously developing PBPK models to comprehensively evaluate and compare exposures to organic compounds from either contaminated soil or water.

Plutonium and uranium residues (e.g., incinerator ash, combustibles, and sand/slag/crucibles) resulting from the purification and processing of nuclear materials constitute an enormous volume of ''lean'' processing waste and represent a significant fraction of the U. S. Department of Energy's (DOE) legacy waste from fifty years of nuclear weapons production activities. Much of this material is presently in storage at sites throughout the DOE weapons production complex (most notably Rocky Flats, Savannah River and Hanford) awaiting further processing and/or final disposition. The chemical and physical stability of much of this material has been called into question recently by the Defense Nuclear Facility Safety Board (DNFSB) and resulted in the issuance of a mandate by the DNFSB to undertake a program to stabilize these materials [1]. The ultimate disposition for much of these materials is anticipated to be geologic repositories such as the proposed Waste Isolation Pilot Plant in New Mexico. However, in light of the mandate to stabilize existing residues and the probable concomitant increase in the volume of material to be disposed as a result of stabilization (e.g., from repackaging at lower residue densities), the projected storage volume for these wastes within anticipated geologic repositories will likely be exceeded simply …

The general aim of this project is to design and implement a new sensor technology that offers the unprecedented levels of specificity needed for analysis of the complex chemical mixtures found at USDOE sites nationwide. The new sensor concept combines the elements of electrochemistry, spectroscopy and selective partitioning into a single device that provides three levels of selectivity. We have had three major goals: Demonstration of the general sensor concept on seven model systems; Development of a prototype sensor for ferrocyanide with associated instrumentation; and Testing prototype sensor for ferrocyanide on waste tank simulant (U-Plant-2 Simulant Solution) provided by PNNL and then on actual tank waste (Tank 241-C-112) at PNNL/Hanford

This project investigates the in-situ degradation of semivolatile organic compounds (SVOCs) and volatile organic compounds (VOCs) using in-well sonication, in-well vapor stripping, and bioremediation. Pretreating groundwaters with sonication techniques in-situ would form VOCs that can be effectively removed by in-well vapor stripping and bioremediation. The mechanistic studies focus on the coupling of megasonics and ultrasonics to ''soften'' (i.e., partially degrade) the SVOCs; oxidative reaction mechanism studies; surface corrosion studies (on the reactor walls/well); enhancement due to addition of oxidants, quantification of the hydroxyl radical formation; identification/quantification of degradation products; volatility/degradability of the treated waters; development of a computer simulation model to describe combined in-well sonication/in-well vapor stripping/bioremediation; systems analysis/economic analysis; large laboratory-scale experiment verification; and field demonstration of the integrated technology. Benefits of this approach include: (1) Remediation is performed in-situ; (2) The treatment systems complement each other; their combination can drastically reduce or remove SVOCs and VOCs; (3) Ability to convert hard-to-degrade organics into more volatile organic compounds; (4) Ability to remove residual VOCs and ''softened'' SVOCs through the combined action of in-well vapor stripping and biodegradation; (5) Does not require handling or disposing of water at the ground surface; and (6) Cost-effective and improved efficiency, resulting in shortened …

Incomplete or sparse information on types of data such as geologic or formation characteristics introduces a high level of risk for oil exploration and development projects. ''Expert'' systems developed and used in several disciplines and industries, including medical diagnostics, have demonstrated beneficial results. A state-of-the-art exploration ''expert'' tool, relying on a computerized data base and computer maps generated by neural networks, is proposed for development through the use of ''fuzzy'' logic, a relatively new mathematical treatment of imprecise or non-explicit parameters and values. Oil prospecting risk can be reduced with the use of a properly developed and validated ''Fuzzy Expert Exploration (FEE) Tool.'' This tool will be beneficial in many regions of the US, enabling risk reduction in oil and gas prospecting and decreased prospecting and development costs. In the 1998-1999 oil industry environment, many smaller exploration companies lacked the resources of a pool of expert exploration personnel. Downsizing, low oil prices and scarcity of exploration funds have also affected larger companies, and will, with time, affect the end users of oil industry products in the US as reserves are depleted. The proposed expert exploration tool will benefit a diverse group in the US, leading to a more efficient use …

Biofiltration systems can be used for treatment of volatile organic compounds (VOCs); however, the systems are poorly understood and are normally operated as ''black boxes''. Common operational problems associated with biofilters include fouling, deactivation, and overgrowth, all of which make them ineffective for continuous, long-term use. The objective of this investigation was to develop generic methods for long-term stable operation, in particular by using selective limitation of supplemental nutrients while maintaining high activity. As part of this effort, we have provided a deeper fundamental understanding of the important biological and transport mechanisms in biodestruction of sparingly soluble VOCs and have extended this approach and mathematical models to additional systems of high priority EM relevance--direct degradation and cometabolic degradation of priority pollutants such as BTEX and chlorinated organics. Innovative aspects of this project included development of a user-friendly two-dimensional predictive model/program for MS Windows 95/98/2000 to elucidate mass transfer and kinetic limitations in these systems, isolation of a unique microorganism capable of using sparingly soluble organic and chloroorganic VOCs as its sole carbon and energy source, and making long-term growth possible by successfully decoupling growth and degradation metabolisms in operating trickle bed bioreactors.

The goal of this project was to expand the range of chemical species that may be detected by membrane introduction mass spectrometry (MIMS) in environmental, and specifically in Mixed Waste, monitoring and characterization applications. Membrane introduction mass spectrometry (MIMS) functions as a near real-time monitor: there is little to no sample preparation and t analysis time is seconds to minutes. MIMS can be implemented as a flow injection technique, where samples, standards, and method blanks can be sequentially analyzed in a continuous fashion. The membrane acts as an interface between the sample (air or water) and the vacuum of the mass spectrometer. Transport of the analyte through the membrane occurs by the process of pervaporation. This process is described by adsorption to the outer surface of the membrane, diffusion through the membrane, and desorption from the inner membrane surface into a helium gas flow or into vacuum. The driving force for this work is the need for a rapid, sensitive, and broadly applicable tool for characterizing organic and metal-containing contaminants in a variety of DOE (and other) waste streams. In all characterization scenarios, a balance must be struck between evaluation of the hazards and their extent at a waste site, …

In order to realize the full potential of bioremediation, an understanding of microbial community and individual bacterial responses to the stresses encountered at contaminated sites is needed. Knowledge about genetic responses of soil and subsurface bacteria to environmental stresses, which include low nutrients, low oxygen, and mixed pollutants, will allow extrapolation of basic principles to field applications, either using indigenous bacteria or genetically engineered microorganisms. Defining bacterial responses to those stresses presents an opportunity for improving bioremediation strategies, both with indigenous populations and genetically-engineered microbes, and should contribute to environmental management and restoration actions that would reduce the cost and time required to achieve OEM's clean up goals. Stress-inducible genes identified in this project can be used as molecular probes for monitoring performance of indigenous bacteria as well as the effectiveness of bioremediation strategies being employed. Knowledge of survival and catabolic plasmid stability of indigenous bacteria will be needed for devising the most effective bioremediation strategy. In addition, stress-inducible regulatory elements identified in this project will be useful for creating genetically-engineered microorganisms which are able to degrade hazardous wastes under stress conditions at contaminated sites. One of the model organisms, Deinococcus radiodurans, is a stress-resistant bacterium. Thus, in addition to …

Remediation processes frequently involve species possessing limited solubility in water. For this project, we were interested in novel strategies using molecularly modified enzymes with enhanced activity and stability for remediation of recalcitrant compounds in organic solvents. Performance of naturally occurring enzymes is usually quite limited in such organic environments. The primary objective of the work was to gain a fundamental understanding of the molecular and catalytic properties of enzymes that have been chemically modified so that they are catalytically active and chemically stable in organic solvents. The premise was that stabilized and activated enzymes, which can function under harsh chemical conditions, are optimally suited for bioremediation in nonaqueous media where substrates of interest are more soluble and processed with greater efficiency. This unique strategy was examined with respect to the degradation of chlorophenols and PCBs.

The goal of the proposed research is to develop new chemistry for the removal of organic contaminants from supercritical carbon dioxide. This has application in processes used for continuous cleaning and extraction of parts and waste materials. Cleaning and extraction using supercritical carbon dioxide (scCO2) can be applied to the solution of a wide range of environmental and pollution prevention problems in the DOE complex. The objectives at the outset of the project were to: (1) determine if photocatalytic or other clean oxidation chemistry can be applied to the removal of organic or inorganic contaminants that are introduced into supercritical carbon dioxide during its use as an extraction and cleaning medium. The target will be contaminants left in solution after the bulk of solutes have been separated from the fluid phase by changing pressure and/or temperature (but not evaporating the CO2). This is applicable to development of efficient separations and will strengthen pollution prevention strategies that eliminate hazardous solvents and cleaning agents. (2) explore the use of supercritical carbon dioxide as a solvent for the photocatalytic oxidation of organic compounds and to compare it to other types of oxidation chemistry. This will add to the fundamental understanding of photocatalytic oxidation …

The objective of this research was to develop fundamental understanding and predictive models of radiation effects in glasses and ceramics at the atomic, microscopic, and macroscopic levels, as well as an understanding of the effects of these radiation-induced solid-state changes on dissolution kinetics (i.e., radionuclide release). The research performed during the duration of this project has addressed many of the scientific issues identified in the reports of two DOE panels [1,2], particularly those related to radiation effects on the structure of glasses and ceramics. The research approach taken by this project integrated experimental studies and computer simulations to develop comprehensive fundamental understanding and capabilities for predictive modeling of radiation effects and dissolution kinetics in both glasses and ceramics designed for the stabilization and immobilization of high-level tank waste (HLW), plutonium residues and scraps, surplus weapons plutonium, other actinides, and other highly radioactive waste streams. Such fundamental understanding is necessary in the development of predictive models because all experimental irradiation studies on nuclear waste materials are ''accelerated tests'' that add a great deal of uncertainty to predicted behavior because the damage rates are orders of magnitude higher than the actual damage rates expected in nuclear waste materials. Degradation and dissolution processes …

The major technical objectives of this program are threefold: (1) to develop the design tools and a fundamental understanding of the fluid dynamics of a slurry bubble column reactor to maximize reactor productivity, (2) to develop the mathematical reactor design models and gain an understanding of the hydrodynamic fundamentals under industrially relevant process conditions, and (3) to develop an understanding of the hydrodynamics and their interaction with the chemistries occurring in the bubble column reactor. Successful completion of these objectives will permit more efficient usage of the reactor column and tighter design criteria, increase overall reactor efficiency, and ensure a design that leads to stable reactor behavior when scaling up to large-diameter reactors. Washington University's work during the reporting period involved the implementation of the automated calibration device, which will provide an advanced method of determining liquid and slurry velocities at high pressures. This new calibration device is intended to replace the original calibration setup, which depended on fishing lines and hooks to position the radioactive particle. The report submitted by Washington University contains a complete description of the new calibration device and its operation. Improvements to the calibration program are also discussed. Iowa State University utilized air-water bubble column …

At many DOE facilities, the presence of radioactive wastes and other contaminants within the vadose zone poses a serious and ongoing threat to public health and safety. In many cases these contaminants have been introduced directly to the vadose zone through releases on the surface or in shallow pits, and through leaking storage facilities. To reduce the environmental risks these wastes pose, the DOE is currently considering two fundamentally different approaches. The first involves remediation by treating contaminants in-place while the second, and more economically feasible being examined by DOE, involves in-situ immobilization of the wastes. Immobilization would be achieved through both injection of subsurface grout barriers to block transport pathways and installation of surface caps to prevent additional water infiltration into contaminated formations. A necessary requirement of both remediation approaches is the need to obtain information on the spatial distributions of the hydraulic and transport properties, the amount of contamination in place, and flow and transport processes that are occurring. With this information in hand, informed decisions can be made in order to optimize the remediation process for each particular case. In particular, these capabilities could result in reduced remediation costs, as well as providing necessary data to illustrate …