'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 …

'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. …

'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.'

'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.'

A grant, �Improved Efficiency of Miscible CO2 Floods and Enhanced Prospects for CO2 Flooding Heterogeneous Reservoirs,� DOE Contract No. DE-FG26-97BC15047, was awarded and started on June 1, 1997. This project examines three major areas in which CO2 flooding can be improved: fluid and matrix interactions, conformance control/sweep efficiency, and reservoir simulation for improved oil recovery. In this quarter we continued the examination of synergistic effects of mixed surfactant versus single surfactant systems to enhance the properties of foams used for improving oil recovery in CO2 floods. The purpose is to reduce the concentration of surfactants and find less expensive surfactants. Also, we are refining reservoir models to handle the complex relationships of CO2-foam and heterogeneous reservoirs. The third area of our report this quarter comprises the results from experiments on CO2-assisted gravity drainage in naturally fractured oil reservoirs. Two more CO2 core flood experiments have been conducted under reservoir conditions to investigate the effect of pressure on oil recovery efficiency during CO2-assisted gravity drainage.

'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.'

'Soil samples from three industrial sites at two depths ranges (2--4 feet and 8--14 feet) were received and pertinent physico-chemical properties, such as pH, specific surface area, moisture content, organic matter content, hydraulic conductivity, cation exchange capacity (CEC), pH at zero point of charge (pH{sub zpc}), particle size distribution, organic contaminants and heavy metals fractionation were analyzed. Results show that clay and silt are the major components in the soil samples, which exhibits a relatively low hydraulic conductivity of about 10{sup -7} {approximately} 10{sup -8} cm/sec. The pH value of soil samples is in the neutral range (from pH 6.1 to 7.6) and its variation with depth is insignificant. Organic matter content is another important factor which affects soil properties such as specific surface area, chemical adsorption capacity and cation exchange capacity. Results indicate that the organic matter content ranges between 0.79% and 1.81%. The effective cation exchange capacity is from 13.8 to 21.2 meq/100 g. The values of moisture content, specific surface area and pH{sub zpc} range from 10.2--16.9%, 0.4--0.9 (m{sup 2}/g) and 2.18--2.60, respectively.'

'The authors have begun to examine the extraction and recovery of heavy elements from aqueous waste streams using redox-active metal chalcogenides. They have been able to prepare extractants from known chalcogenide starting materials, studied the efficacy of the extractants for selective removal of soft metal ions from aqueous phases, studied the deactivation of extractants and the concomitant recovery of soft metal ions from the extractants, and characterized all of the solids and solutions thus far in the study. The study was proposed as two parallel tasks: Part 1 and Part 2 emphasize the study and development of known metal chalcogenide extractants and the synthesis and development of new metal chalcogenide extractants, respectively. The two tasks were divided into sub-sections that study the extractants and their chemistry as detailed below: Preparation and reactivity of metal chalcogenide host solids Extraction of target waste (guest) ions from simulated waste streams Examination of the guest-host solids recovery of the guest metal and reuse of extractant Each section of the two tasks was divided into focused subsections that detail the specific problems and solutions to those problems that were proposed. The extent to which those tasks have been accomplished and the continued efforts of the …

'The objectives of this report are: (1) To investigate the development of Raman spectroscopy for remote, in-situ, real-time measurement of the processes underlying chemical corrosion of glasses, (2) To conduct Raman spectroscopy measurements and quantum mechanical modelling studies of the transition states, corrosion products, and transition state energies for the hydrate species of higher valence and multivalent ions formed in the reconstructed glass surface. (3) To use these results to model long-term corrosion behavior of complex borosilicate wasteform glasses. (4) To apply the Raman spectroscopy and modelling methods developed here for the remote analysis of leaching processes in waste glasses containing radioactive components, and for imaging of variations in leaching behavior due to composition inhomogeneities in large scale waste glass products. Results of First Year Research During the first year, the authors primarily addressed Objective (1) which is to develop a methodology for the remote monitoring of leaching processes in glasses by Raman spectroscopy. The authors assembled a micro and macro Raman system for examining surface structure in glass samples, in-situ within the leaching vessel. The Raman spectrometer was prepared for imaging by installing a CCD detector which gives 2-dimensional information. The latter can be used to obtain spectrographic data …

'It is the objective of this proposed study to develop and field test a new, integrated Hybrid Hydrologic-Geophysical Inverse Technique (HHGIT) for characterization of the vadose zone at contaminated sites. This fundamentally new approach to site characterization and monitoring will provide detailed knowledge about hydrological properties, geological heterogeneity and the extent and movement of contamination. HHGIT combines electrical resistivity tomography (ERT) to geophysically sense a 3D volume, statistical information about fabric of geological formations, and sparse data on moisture and contaminant distributions. Combining these three types of information into a single inversion process will provide much better estimates of spatially varied hydraulic properties and three-dimensional contaminant distributions than could be obtained from interpreting the data types individually. Furthermore, HHGIT will be a geostatistically based estimation technique; the estimates represent conditional mean hydraulic property fields and contaminant distributions. Thus, this method will also quantify the uncertainty of the estimates as well as the estimates themselves. The knowledge of this uncertainty is necessary to determine the likelihood of success of remediation efforts and the risk posed by hazardous materials. Controlled field experiments will be conducted to provide critical data sets for evaluation of these methodologies, for better understanding of mechanisms controlling contaminant …

'A team from two national laboratories is studying transmutation effects in crystalline waste forms. Analyses are being done with 18 year old samples of {sup 137}Cs-bearing pollucite (CsAlSi{sub 2}O{sub 6} \267 0.5 H{sub 2}O) obtained from a French company. These samples are unique in that the pollucite was made with various amounts of {sup 137}Cs, which was then sealed in welded stainless- steel capsules to be used as tumor irradiation sources. Over the past 18 years, the {sup 137}Cs has been decaying to stable Ba in the capsules, i.e., in the absence of atmospheric effects. This material serves as an analogue to a crystalline waste form in which such a transmutation occurs to possibly disrupt the integrity of the original waste form. Work this year consisted of determining the construction of the capsule and state of the pollucite in the absence of details about these components from the French company. The authors have opened one capsule containing nonradioactive pollucite. The information on the construction of the stainless-steel capsule is useful for the work that the authors are preparing to do on capsules containing radioactive pollucite. Microscopic characterization of the nonradioactive pollucite revealed that there are at least two compounds in …

'Vadose regimes can be the sites of complex interactions between the atmosphere and groundwater. When a volatile contaminant exists as free product or in dissolved form in the vadose environment, upward transport can occur with the contaminant ultimately being vented as a vapor into the atmosphere. This transport happens naturally and can be enhanced by anisotropy resulting from heterogenities in the vadose regime. Several stages in the transport process are involved in going from a volatile, liquid state contaminant to a contaminant vapor vented at the surface. In a three-year effort, called the Vadose Zone Transport Study, the authors are investigating, with the aid of existing data, new field studies involving dissolved tracer gases and 3-D diagnostic computer simulations that provide a framework to interpret the observations, the detailed nature of each of these stages of transport in several different kinds of vadose regimes. They are emphasizing the impact of features specific to a site, that is, the local geology and hydrology, on each stage of the transport process. In particular they want to better understand how the time scales for (1) partitioning contaminants from the liquid to the vapor states and then (2) transporting the vapor out of the …

'Electromagnetic induction tomography is a promising new tool for imaging electrical conductivity variations in the earth. The EM source field is produced by induction coil (magnetic dipole) transmitters deployed at the surface or in boreholes. Vertical and horizontal component magnetic field detectors are deployed in other boreholes or on the surface. Sources and receivers are typically deployed in a configuration surrounding the region of interest. The goal of this procedure is to image electrical conductivity variations in the earth, much as x-ray tomography is used to image density variations through cross-sections of the body. Although such EM field techniques have been developed and applied, the algorithms for inverting the magnetic data to produce the desired images of electrical conductivity have not kept pace. One of the main reasons for the lag in the algorithm development has been the fact that the magnetic induction problem is inherently three dimensional: other imaging methods such as x-ray and seismic can make use of two-dimensional approximations that are not too far from reality, but the author does not have this luxury in EM induction tomography. In addition, previous field experiments were conducted at controlled test sites that typically do not have much external noise …

'Preparations have been made to collect groundwater samples from the unconfined Pleistocene aquifer on Long Island, N.Y. from wells at Brookhaven National Lab.. Dr. Jan Naidu of the Brookhaven Safety and Environmental Protection Division has been intimately involved with the groundwater monitoring program at the site for many years, and has provided us with detailed information regarding site hydrogeology, groundwater chemistry, and monitor well locations and construction. In consultation with Dr. Naidu, a series of wells have been chosen for sampling that extend over a distance of {approximately}5000 feet along a single flow path, with estimated water ages of up to {approximately}20 years. Since the recharge area for these waters has been the source of low levels of tritium (and possibly {sup 90}Sr) contamination, there has been considerable interest in the hydrogeology and chemistry of the area, and all information gathered at the site will be provided to BNL staff. Groundwater sampling is planned for the autumn of 1997. At this time, aquifer materials will also be obtained from the drill core repository of the USGS office in Long Island, where Mr. Henry Ku has indicated that material will be available for the use. As a complement to the studies …

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'The main scope of this work is to: (1) develop a novel tomographic ultrasonic technique to obtain the real-time distribution of acoustic velocity and flow velocity; (2) use nuclear magnetic resonance imaging (NMRI) to measure velocity profiles and rheological properties of complex fluids and suspensions; (3) establish a facility for making laser Doppler velocimetry (LDV) measurements that can be The overall goal is to obtain real-time rheology and solids concentration within a solid-liquid suspension flowing in a pipeline. To nondestructively obtain the rheology of the fluid flowing in a pipe, accurate measurement of local shear rate distribution is required. This objective was met by using two real-time tomographic techniques: an ultrasonic Doppler velocimetry system and an NMRI system. The first method combines the existing state-of-the-art ultrasonic velocimetry technology base with a novel tomographic concept to non-intrusively obtain high resolution acoustic and flow velocity profile at a section of the flow field. The acoustic velocity profile provides a means of improving the flow velocity measurement accuracy. These data are also, used to yield the profile of solids concentration. In addition, the volumetric flow rate was determined from integration of the velocity profile. From the knowledge of the concentration profile the mass …

'Acoustic probes have shown promise to be quite effective in determining the solid content in solid-liquid suspensions. However, the presence of small amounts of gas in the waste slurries stored in tanks across the DOE complex prevents straightforward application for characterization of these slurries. The proposed research will develop an acoustic probe for monitoring particle size and volume fraction in slurries in the absence and the presence of gas bubbles. Theoretical Analysis Accomplished: Attenuation of sound waves depends on the size distribution of the solids and the volume fraction of solids. These can in principle be calculated from attenuation measured over a range of frequencies. However, small amounts of bubbles distort the measured attenuation. A typical result from theoretical analysis for the attenuation of solid- gas-liquid systems is given in Figure 1. The total attenuation of a sound wave v(o) equals the sum of contributions by a large number of ''bins'' of particle sizes. This notion yields the following equation for the (hitherto) unknown number density of solid particles as a function of particle radius N(a): j k(o,a)N(a)da = v(o), where the kernel k(o,a) is obtained from analysis. If N(a) is given, the above equation is used to calculate the …

'There is a fundamental knowledge gap associated with the in situ remediation of non-aqueous phase pollutants. Currently it is not possible to accurately determine the interfacial surface area of non-aqueous contaminants. As a result it is impossible to (1) accurately establish the health and environmental risk associated with the pollution: (2) precisely quantify and evaluate the potential efficacy of various in situ treatment technologies; and (3) conduct reliable performance assessments of the applied remediation technology during and after the clean-up. The global goal of this investigation is to try to remedy these shortcomings through the development of a formalized functional relationship between interfacial area (a), phase saturation (S) and capillary pressure (P). The development of this relationship will allow the direct determination of the fluid-fluid interfacial area from field measurements. Quantitative knowledge of the surface area of the non-aqueous phase pollutant facilitates accurate predictions of both the rate of dissolution and the contact area available for treatment. In addition. if saturation and capillary pressure measurements are made during the remediation process. both the spatial and temporal effectiveness of the remediation technology can be quantified. This information can then be used to optimize the restoration program. The project objective will be …