Projects
TThe Environmental and Water Studies Program encompasses both teaching and research. The research program emphasizes several major areas of activity and, as a general philosophy, promotes interdisciplinary projects. Laboratory research is generally conducted within the Environmental Fluid Mechanics Laboratory and the Water Quality Control Laboratory. Often faculty, staff and students from several specialty areas work as a team on a given research endeavor. Student participation is a vital element; at any one time, approximately forty graduate students, representing all levels of degree candidacy, are contributing to one or another of the approximately twenty-five funded research projects. The size and diversity of the research program provide numerous learning opportunities outside the classroom, and stimulate a level of excitement for learning through research that is rare. Student-faculty relations are relaxed and friendly. Student initiative is encouraged in conceiving and conducting research, as well as in communicating results. Current research includes laboratory and field studies on the movement and fate of organic and inorganic compounds in ground water and surface waters; physical, chemical, and biological processes and mechanisms responsible for the release, transport, transformation, and retention of contaminants; contaminant control processes (especially the removal of trace contaminants); mathematical modeling of important processes as well as hydrologic phenomena; stochastic modeling of spatial variability and uncertainty in ground water flow and transport; the development of alternative energy sources; fundamental principles of physical, chemical and biological treatment technologies for water, waste water and solid wastes. In the environmental fluid mechanics area current research is focused on stratified flows in lakes, reservoirs, natural and forced convection flows in energy systems, and simulation of mesoscale phenomena in the oceans and surface layers of the atmosphere. Other research includes hydrologic modeling, interaction between surface water and ground water, and a comprehensive program on the fundamentals of fluid transport, including turbulence and mixing in natural water bodies and the mechanism of dispersion in porous media flows. In the environmental planning and management area current research is focused on implementation of environmental policies and programs in developing countries and on the applications of expert systems in operating water resources systems. The following is a list of currently active externally funded research projects:

Topic:
Environmental Fluid Mechanics
Hydrology and Water Resources
Transport and Fate of Contaminants in the Atmosphere
Transport and Fate of Contaminants in Groundwater
Contaminant Control Technology
Environmental Planning and Management
Environmental Microbiology

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Environmental Fluid Mechanics

Hydrology and Water Resources

The Water Supply of the Bay Area during Prolonged Droughts - Kitanidis, P. K. (UPS Foundation)
The economy of the Bay Area has been booming and new housing developments can be found to the edges of the Central Valley. Is there sufficient water to support the existing population and such development rates? The purpose of this research is to study the sources, availability, and reliability of water for the greater San Francisco Bay Area, with emphasis on drought conditions. An additional objective is to evaluate the need for gradual water rationing as a drought progresses. The project includes statistical analysis of time series of major sources, demand projections, the study of conservation and rationing policies, and the conjunctive use of groundwater and surface water.

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Conditioning Model Predictions on Data and Solution of Inverse Problems in Contaminant Hydrogeology - Kitanidis, P. K.
It is difficult to predict pollutant concentration in geologic formations. However, by making sensible use of data, one can improve the accuracy of predictions of models of mass transport and chemical fate. In practice, the available observations are not sufficient for predicting a unique scenario, as in the deterministic approach. The probabilistic approach aims to simulate an ensemble of scenarios that are consistent with the physical laws that govern representations of the flow, transport, and transformation, as well as the available observations. These predictions are useful in risk analysis and management, such as selecting the most cost-effective remediation scheme or sampling strategy. We develop and test new methods for incorporating the information contained in observations to: (a) Estimate hydrogeologic parameters that control rates of groundwater flow and the transport and transformation of chemicals in the subsurface, (b) Generate an ensemble of equally likely chemical concentrations consistent with process understanding and observations.

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Management of Stochastic Dynamic Systems with Emphasis on Reservoir Operation - Kitanidis, P. K.
Even when existing water-resource systems are managed efficiently, it is hard for trial-and-error heuristic management to keep up with changing demands and management objectives. Mathematical modeling and optimization could contribute to improved management, but existing procedures are limited in their effectiveness and acceptance, partially because they do not account properly for hydrologic and demand uncertainty. However, recent advances in algorithms and increases in computer power have made some problems tractable without resorting to inappropriate simplifying assumptions. We have been working to develop and apply methods that allow treatment of previously unsolvable optimization problems, including the conjunctive management of groundwater and surface water systems. The algorithms we have developed for multi-dimensional stochastic dynamic programming problems are the fastest available.

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Transport and Fate of Contaminants in the Atmosphere

Effects of Future Emissions and a Changed Climate on Urban Air Quality - Jacobson, M.Z. (EPA). This is project to study the effects of changes in emissions on climate and the resulting feedback of climate change on air quality in Los Angeles, the Central Valley, and Atlanta during the next 50 years. We will examine the effects of emission changes resulting from standard IPCC-SRES future emission scenarios. We will also examine the effects of emission changes due to implementing a future fleet of ethanol-gasoline, plug-in gasoline-electric hybrids, and wind-electrolysis-hydrogen-fuel-cell vehicles. Finally, we will look at the future contribution of Asian emissions to U.S. pollution. The study will involve model simulations of climate and air quality with GATOR-GCMOM, which nests size-resolved aerosols, gases, and meteorological variables together from the global to urban scale. This model is unique because it allows the continuous inflow of gas and aerosol information from the global to finer scales (rather than running a separate global model offline to produce meteorology a regional nested model) and treats physical processes and gridding consistently on all scales. The model resolves transports (horizontally and vertically) clouds and precipitation and forms them physically from aerosol particles on nonglobal nested grids. The model will first be used with 50-year A1B and B1 emission factors applied to the 2005 U.S. National Emission Inventory. Three additional future inventories, one with E85 (85% ethanol-15% gasoline) vehicles, one with plug-in hybrid vehicles, and one with wind-hydrogen fuel cell vehicles substituted for gasoline vehicles, will also be prepared. Simulations will be run for 50 years, with nesting in Los Angeles, the Central Valley, and Atlanta in years 1 and 50. First-year results will be evaluated against data. This study will estimate the effects of future emission scenarios on climate and the resulting climate effects on U.S. air quality. While overall U.S. air quality is expected to improve due to lower emissions, global warming may reduce this benefit. The purpose of this project is to quantify the net effect of global warming on air pollution. The study will also analyze a future fleet of E85 vehicles on 3-D air pollution. Of interest is determination of whether such vehicles will increase or decrease ozone and PAN in different parts of the U.S. and how global warming may affect their emission. Higher future emissions from Asia are hypothesized to increase urban air quality problems in California and the west.

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Studying the effects of aircraft exhaust on global and regional climate - Jacobson, M.Z. and S.K. Lele (FAA)
This is a project to quantify the effects of aircraft exhaust and contrails on global and U.S. climate and atmospheric composition by combining aircraft emission data with nested global-through-regional climate modeling. The nested model to be used will be GATOR-GCMOM (gas, aerosol, transport, radiation, general-circulation, mesoscale, and ocean model). Subgrid-scale information about contrails will be obtained from Large-Eddy Simulation (LES) modeling. Three issues to be examined over the long term are the effects of aircraft exhaust on contrails and their feedback to climate, gas-phase aircraft exhaust on tropospheric/stratospheric chemical composition, and the effect of soot aerosol emissions from aircraft on climate. The rigorous completion of all three of these tasks will take at least three years; however, in the first year, for which funding is requested here, we propose to provide a preliminary quantification of the spatially-distributed effects of aircraft contrails on global climate and, at higher resolution, U.S. regional climate. On both scales, we will provide domain (global and regional)-averaged and spatially-varying statistics and maps of, for example, near-surface temperature changes, surface and top-of-the-atmosphere irradiance changes, and cloud fraction changes due to contrails. Such information will attempt to address the question of the extent to which regional effects of contrails are much more significant than seen in the global average. We will evaluate the model against data to the extent possible, although evaluation is unlikely to be complete within one year. If the project is funded past the first year, the study will extend and improve the LES modeling, examine the effects of contrails at higher resolution and over a longer period over the U.S. with the improved LES results, and address the questions of the effects of aircraft on tropospheric/stratospheric composition and atmospheric heating through soot emissions.

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Indoor Air Pollution and Health in Developing Countries: An Intervention Study in Bangladesh– N.G. Miller and L.M. Hildemann (Environmental Venture Fund, Woods Institute for the Environment)
Half the world's population relies on dung, brush and wood as their primary source of energy for cooking and heating, and biomass combustion indoors is viewed as a major contributor to indoor air pollution in developing countries. Indoor air pollution has been shown to be associated with acute respiratory infections -- in fact, the World Health Organization has attributed 5% of all female deaths in the developing world to indoor air pollution. This project aims to assess the short- and long-term effectiveness of various social and economic incentives at inducing rural villagers in Bangladesh to acquire and use an improved cookstove. The health benefits of the improved cookstove will be assessed by measuring the real-time exposure of the cook to indoor particulate matter (smoke) before and after changing cookstove technologies.

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Indoor Bioaerosols in Home Environments ˆ Hildemann, L. M. (Clorox Company) Individuals in the U.S. spend ~90% of their time indoors, where the concentrations of airborne particles ("bioaerosols") like molds and fungi can be much higher than outdoor levels. This study will measure bioaerosols inside and outside of typical homes, assessing how building characteristics (e.g., flooring type, age of structure) and the behavior of residents (e.g., cleaning frequency, activity level, presence of pets) influence the concentration levels of molds and fungi present.

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Characterization of Particulate Matter Generated from the Operation of Motor Vehicles – Hildemann, L. M. (Ford Research Foundation) Increasing regulations on particulate matter (PM) emissions over the next decade are expected to impact the motor vehicle industry. A major issue.is whether these new regulations will be based on the mass, the number,or the chemical composition of the PM. This research will examine and develop new technologies for measuring the chemical composition of PM in modern-day motor vehicle emissions.

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Studying the Mixing State of Aerosols and Its Impact on Global Climate – Jacobson, M. Z. (NSF) The goal of this project is to analyze the effect of the mixing state of aerosols on global and regional direct forcing and temperatures. One scientific question to be addressed is, what is the global- and regional-scale mixing state of aerosol-particles and what is the resulting direct radiative forcing? A second question is, which feedbacks of aerosol-particles to climate are important and which ones are not? A third question is, what are the climate effects of (a) fossil-fuel soot and organic matter, (b) biomass burning gases and particles, (c) sulfur dioxide and resulting sulfate, and how do the effects of these components compare with the effects of CO2 and CH4?

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Studying the Effects of Ca, Mg, and K on Aerosol Size and Composition, NOy, and Radiative Transfer – Jacobson, M. Z. (NASA). This is a project to study the effects of calcium, magnesium, and potassium on aerosol size and composition. These chemicals, present in soil dust and/or sea spray, have been found to have an important effect on aerosol size distributions in and relatively clean air, shifting nitrate from the coarse mode to the accumulation mode. For this study, the feedback between these chemicals on radiative parameters, such as UV, total solar, and infrared irradiance and top-of-the-atmosphere radiative forcing will be examined. The calculations will also be coupled with gas-phase chemistry to estimate the effects of Ca, Mg, K, and total aerosols on gas-phase NOy concentrations. The purpose of this exercise is to estimate the extent to which aerosols as a whole and individual aerosol components affect the NOy:NOx ratio, which is typically overpredicted in many models.

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Studying the effects of source-specific gas and particulate emissions on global climate and atmospheric composition – Jacobson, M.Z. (NASA) This is a project to study the effects of controlling current and future anthropogenic gas and particulate emissions on global climate and atmospheric composition. The proposal involves the development of current and future global anthropogenic gas and particulate emission inventories by source category and the global simulation of the climate response and atmospheric composition resulting from changes in emissions. The overall goal of the study is to improve our understanding of the effects of different gas and particle emission sources on climate and on atmospheric composition. The research is a collaborative effort among scientists at Stanford University and Argonne National Laboratory. For this study, up-to-date and estimated future global emission inventories for all important gas and particle components from biomass burning, coal, natural gas, biofuel, diesel, and gasoline, will be developed. The inventories will be used, together with existing inventories from other gas and particle sources, in an air-pollution/climate model to examine effects on global climate and atmospheric composition. Such a study is important from a scientific and policy perspective. It will try to address questions such as, what are the time-dependent combined effects of biomass-burning gases and aerosol particles on climate and what are the time-dependent climate effects of combined gas- and aerosol particle emissions from diesel vehicles, gasoline vehicles, power plants, and indoor biofuel/coal burning. This study will also enable an examination of the global distribution of gas and particle components. It will allow an examination of the climate response of nitrogen oxide (NOx) and reactive organic gas (ROG), methane, and carbon monoxide emissions through their feedback to tropospheric ozone and secondary particulate matter.

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Using satellite data and models to study the effect of global climate on regional pollution and vice versa – Jacobson, M.Z. (NASA) This is a project to use satellite data with models to examine the effects of regional pollution on the global atmosphere and the effects of global chemical and climate change on regional air quality. The project involves three major task areas: gathering and gridding appropriate satellite and in-situ data for comparison with models, comparing models on the global and regional scales with the satellite retrievals and the in-situ data, and using the models to address the main issue listed. The effect of global chemical and climate change on regional air quality will be evaluated with a nested global-through-urban scale air pollution/climate/weather forecast model. Baseline simulations for 2001 will be run and compared with satellite retrievals, sounding data, and with data from a network of several thousand near-surface monitoring stations. The global portion of the model will then be applied to simulate changes in climate over multiple years due to estimated changes in greenhouse gas and particulate emissions determined from Special Report on Emission Scenarios (SRES) scenarios. The effects of climate change on air pollution in the nested grids will be evaluated in years 20 and 50. Simulations will be affected by estimated changes in future global emissions. The effects of regional pollution on the global atmosphere will be examined by first comparing results from two regional models with satellite data and in-situ measurements from a field campaign, then examining the fate of the pollutants as they exit from the urban/regional to larger scale. Sensitivity tests will be run under both current and future climate and emission conditions to examine the relative importance of different organic gases, emitted on the urban/regional scale, on export of ozone and aerosols to the large scale. Sensitivity tests will also examine the effect of model grid resolution and subgrid treatment on ozone and aerosols venting and dilution from the urban to larger scales.

Exposure to Secondhand Smoke: Effects of Proximity -- Hildemann, L.M. (Tobacco-Related Diseases Research Program) The level of secondhand smoke to which an individual is exposed depends on that person's proximity to the smoker, as well as on the fluid mechanics of the environment. This field project will measure the magnitude of the near proximity effect in typical indoor and outdoor environments, over a length scale of a few meters, using a large array of real-time carbon monoxide monitors. These data will be used to develop a model that accounts for the proximity effect as well as background concentration levels in predicting smoke concentration levels as a function of location relative to a smoker, and this model will be tested via experiments with actual smokers.

Human Exposure Analysis for Pollutants from Secondhand Smoke -- Hildemann, L.M. (Flight Attendant Medical Research Institute) This project will test and develop the utilization of real-time particle monitors for assessing tobacco smoke concentrations in indoor environments where there is smoking. Measurements will be taken of airborne particle concentrations as a function of distance from both smolder-smoked cigarettes and actual smokers. Comparisons will be made between CO and PM levels to assess whether turbulent or molecular diffusion dominates dispersion processes in the indoor environment. With these and other data, an Incremental Exposure model will be developed to assess how different microenvironments and/or proximities to smoking activities contribute to a person's daily exposure to secondhand smoke..

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Transport and Fate of Contaminants in Groundwater
Analysis of Halogenated Organic Particle-Scale Desorption via Column Studies and C-13 Solid State NMR Spectroscopy - Reinhard, M. (EPA)
Research has shown that a significant fraction of organics sorbed to soils and sediments (geosorbents) resists desorption. This fraction is not amenable to conventional treatment and needs special consideration in fate and transport assessment. In this project we identify sorbent properties that govern slow desorption and compare results of desorption studies with predictions based on mechanistic models. The approach is to artificially contaminate geosorbents with TCE, deuterated TCE and/or PCE either individually or as mixtures and to quantify rate of desorption as a function of initial sorbent loading and desorption conditions. Data suggest that the sorption sites of the slow desorbing fraction reside in micropores and that diffusion of is sterically hindered.

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Field-Testing of Palladium-Catalyzed Hydrogenation for Chlorinated Hydrocarbon Removal - Reinhard, M. and Roberts, P.
This project aims to evaluate palladium catalyzed hydrodehalogenation using hydrogen gas as a method for removing halogenated hydrocarbon compounds form contaminated water. Preliminary studies indicate that hydrodehalogenation proceeds under mild conditions when facilitated by a palladium catalyst. The project goal is to gain operational experience with the H2/Pd process under field conditions. Specifically we aim to: 1) quantify catalyst efficacy; 2) identify and minimize the factors contributing to catalyst fouling; 3) measure competing reactions and determine their hydrogen consumption; 4) evaluate the need for pretreatment; and 5) determine how best to supply hydrogen safely and economically. Results will be used to optimize the process, provide design criteria, and evaluate cost effectiveness compared with alternative treatment methods.

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The Fate and Transport of Wastewater Indicator Compounds During Groundwater Recharge with Water of Wastewater Origin - Reinhard, M. (Orange County Water District).
In many water-short areas treated effluents are often the only alternative to augment existing water supplies. Increasingly, effluents are treated so that they can be percolated into the ground to augmented depleted aquifers. This project aims to assess the microbial, chemical and physical processes that affect the fate and transport of anthropogenic contaminants during water percolation and groundwater transport. The data will be useful for developing models that predict the water quality of recharge water as a function of source water quality, soil type, residence time in the ground, and travel distance. Such models will serve to develop science-based regulations for artificial water reuse operations.

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Diffusional Rate Limitations in Heterogeneous Porous Media: Model Structure, Scale, and Geologic Characterization - Freyberg, D.L. and P.V. Roberts (EPA)
This recently completed project focuses on elucidating the nature and environmental significance of both physico-chemical and apparent diffusional rate limitations during solute transport in saturated, heterogeneous porous media, with a view to evaluating the role of diffusional limitations in contaminant remediation. The research considers the relative importance of diffusion and slow advection manifested over a range of spatial scales, from the grain scale up to regional scales, within the context of analytical and numerical transport models that account for advection, diffusion, dispersion, and sorption.

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Strategies for Maintaining Open Water in a Rapidly Sedimenting, Small Reservoir - Cohen, P.S. and D.L. Freyberg (Packard Foundation)
Searsville Lake is a small reservoir on Stanford's Jasper Ridge Biological Preserve which is rapidly filling with sediments from the Corte Madera Creek watershed. The reservoir provides important avian habitat and is used actively in both research and teaching at the Preserve. This project is exploring opportunities to manage the sediment flux tthrough Searsville Lake so that a modest amount of open water can be maintained in the reservoir.

Assessing the Water Balance for Large Ephemeral Streams in Arid Environments - Freyberg, D.L. (USGS student support)
Ephemeral channels in arid and semi-arid environments are an extremely important hydrologically and ecologically. Flow in ephemeral channels is complex, involving short, rapidly rising and falling hydrographs, significant sediment and debris transport, and nearly complete infiltration of the flow over a channel reach. Closely coordinated with an ongoing USGS field data collection project, this dissertation research couples field data with numerical modeling in an attempt to better characterize and predict groundwater recharge from ephemeral channels.

Engineering Pedagogy--Teaching Turbulent Diffusion in Engineering Fluid Mechanics - Freyberg, D.L. and J.R. Koseff (NSF student support)
This doctoral research project focuses on the pedagogy of engineering fluid mechanics, in particular, teaching and learning the concept of turbulent diffusion. Closely coupled with laboratory research studying the role of turbulent diffusion in the foraging behavior of lobsters, this doctoral project is using advances in science education, cognitive science, and psychology, along with carefully designed experimentation and testing, to develop effective teaching techniques for a key, difficult concept in fluid mechanics.

Characterization and Modeling of Sorption Processes for the Nevada Nuclear Waste Storage Investigations - Leckie, J. O. (Los Alamos National Laboratories)
The objectives of this research is to investigate the adsorbtive behavior of the uranyl and neptunyl ions in aqueous systems continuing goethite, hematite and, possibly, feldspars. These studies will include experimental work with competing ligands (e.g., carbonate, EDTA, natural humics) as well as studies to investigate competitive behavior with calcium and magnesium. The resulting data will be modeled using surface complexation models.

Radionuclide Speciation in Heterogeneous Aqueous Geochemical Environment - Leckie, J. O. (Sandia National Laboratory)
This project is concerned with experimental and theoretical studies of the interaction of radionuclides with mineral/solution interfaces likely to be found in the WIPP site high level waste repository. The experimental part involves both time dependent and equilibrium studies of neptunyl and uranyl ion interactions with clays and hydrous iron oxides over a range of ionic strengths (1 x 10-3M - 3M) and in the presence of competing ligands. The theoretical aspects are concerned with the development of modeling approaches for adsorbate interactions with clay surfaces.

Particle-Particle Interactions in Marine Systems: Steady-State, Continuous Flow, Aggregation Studies - Leckie, J. O. (NSF)
Four linked objectives highlight this proposed study of aggregation/sedimentation dynamics. First, a new type of laboratory apparatus will be developed to allow previously unachieved simulation of a continuous flow, steady state system. The simulation apparatus is designed for study of real time aggregation from the simplest processes to relatively complex, biologically mediated processes in controlled, reproducible conditions. Second, two innovative particle size measuring technologies are proposed which allow noninterfering observation of aggregation/sedimentation dynamics. Development and adaptation of these techniques aims at avoiding the sampling artifacts, limited size range and restrictive fluid and particle requirements inherent in many traditional measuring techniques (i.e., electrozone, settling rate). Third, an experimental sequence is suggested which uses controlled variations of particle type, surface chemistry and fluid conditions to assess the interplay of physical, chemical and rudimentary biological factors that have been scantly addressed by previous research. Particular effort is devoted to elucidating both the unique and interactive mechanisms by which exopolymers from selected marine organisms enhance or retard aggregation. Fourth, laboratory findings will be modeled to provide a usable tool for future predictive, design, and analytical work.

Pore-Scale Hydrodynamics and Physicochemical Transport. Constitutive Relations of Solute Transport and Transformation at the Darcy Scale - Kitanidis, P. K. (WRHSRC, NSF, DuPont)
In terms of physico-chemical fundamentals, the transport and transformation of reactive solutes is most satisfactorily understood and quantified at the pore scale. However, this scale is too microscopic for almost all practical applications. In practice, the smallest scale for modeling the transport and chemical fate of solutes in porous media is the laboratory or Darcy scale, which is much larger than the pore scale. At the Darcy scale, a complex medium that actually consists of pores, a solid matrix with biofilm, etc., is replaced by a homogenized medium characterized by constitutive relations among macroscopic variables and parameters. The general advection-dispersion-reaction equation, which is the starting point of every practical modeling effort, is based on these relations and parameters and purports to describe the transport behavior of a concentration spatially averaged over a block of the order of at least centimeters. What is the appropriate form of this equation and what parameters should be used? This research aims at providing answers to these questions. The methodology followed is to model flow, transport, and chemical transformations at the pore scale and then to scale up in order to derive constitutive equations and parameters. The constitutive equations and parameters to be obtained will thus be consistent with the fundamental physico-chemical principles as well as the heterogeneity of the medium. The longer-term objective is to promote a firmer understanding of the factors that control the transport and chemical fate of pollutants, substrates, and electron acceptors at the Darcy scale.

Factors Controlling Solute Dilution in Heterogeneous Formations - Kitanidis, P. K. (NSF, SGF)
Although the effect of heterogeneity on the spreading of contaminant plumes has been studied, the effect of heterogeneity on dilution remains to be determined, especially at "early" times relevant in tracer tests and remediation projects. Dilution is measured by the peak concentration and the volume occupied by solute. Spreading is quantified by the spatial second moment of the concentration distribution. In assessing environmental impacts of groundwater contamination, it is important to be able to anticipate peak concentrations, not just the spatial extent of contamination. We conduct theoretical analysis, detailed numerical simulations, and comparisons with field data. Contaminant dilution measures are related to the porous media constitutive parameters and, primarily, the variability of hydraulic conductivity and the local dispersion. Predictions of dilution are made via analytical approximations, which lead to predictive partial differential equations. The approximations validity is assessed through numerical simulations and the results are evaluated by comparison with results from field experiments. Objectives: (a) a better understanding of the time-evolution of contaminant concentration levels, and (b) guidelines to the practitioner for assessing dilution of contaminants in heterogeneous geologic formations.

Use of In-situ Bioaugmentation for Remediation of an Aquifer Contaminated with Carbon Tetrachloride - Phase III - Criddle, C.S. (Michigan Department of Environmental Quality)
This project involves full-scale demonstration of bioaugmentation for remediation of a site contaminated with carbon tetrachloride. Among the many issues explored are factors affecting transport and competitiveness of a non-native microorganism, carbon tetrachloride degradation, denitrification, chemical delivery, and the role of subsurface heterogeneity.

In Situ Stabilization of Persistent Organic Contaminants in Marine Sediments - Luthy, R.G., U. Ghosh, R.N. Zare and collaborators at the US Army Engineer Research and Development Center, Vicksburg, MS and the University of Notre Dame (US Department of Defense, Strategic Environmental Research and Development Program) The addition of coal-derived sorbents is being evaluated as a treatment technology to reduce the bioavailability and toxicity of polychlorinated biphenyls [PCBs] and polycyclic aromatic hydrocarbons [PAHs] in sediments. This work comprises a suite of tests with contaminated sediment from Hunters Point Naval Shipyard, San Francisco Bay.  

Contaminated Sediment Processes and Bioavailability - Luthy, R.G., S.G. Monismith, D. Epel and R.N. Zare (Stanford University Bio-X Interdisciplinary Initiative Program and collaborators at the US Geologic Survey, Menlo Park, CA) Organic contaminants in sediments pose long-term risks to human health and the environment. This project seeks to understand how the binding of organic contaminants with sediment particles affects the uptake and accumulation of polychlorinated biphenyls [PCBs] and polycyclic aromatic hydrocarbons [PAHs] by particle-feeding organisms, such as clams native to San Francisco Bay.

Characterization of Lampblack Materials in Soils - Luthy, R.G. (Gas Technology Institute, Chicago, IL) Lampblack was produced as a by-product from the former oil gasification processes used in California. The distribution and binding of polycyclic aromatic hydrocarbons [PAHs] in lampblack material from field sites are studied to assess how this material binds the PAHs and reduces exposure.

Microscale Characterization of the Binding and Sequestration of Nitroaromatics in Soils - Luthy, R.G. and U. Ghosh (US Army Engineer Research and Development Center, Vicksburg, MS, and University of Notre Dame) Microscale analytic techniques are applied to soils contaminated with TNT to assess whether crystalline TNT exists in the soil and how this affects the biotreatability of TNT-impacted soils from Army ammunition sites.

PAH and PCB Binding to Sorbent Material - Luthy, R. G. (Ford Motor Company) Mass transfer and phase partitioning studies are evaluating the rate of transfer of PAHs and PCBs from contaminated sediment to sorbent material.

Cyanide Measurement and Chemistry in Wastewater Effluent - Luthy, R. G. (Water Environment Research Foundation and others; with Carnegie Mellon University, Malcolm Pirnie, Inc and Clarkson University) A multi-investigator project is evaluating cyanide measurement and speciation at low levels in chlorinated effluent. The effect of chlorination on possible formation of cyanide at low levels is studied. The collaborators include various large municipal wastewater treatment plants across the United States. (with David A. Dzombak, Carnegie Mellon University)

Mobility of PCBs in Contaminated Soils/Sediments - Luthy, R. G. (US EPA) A novel passive, wick sampler is designed to measure hydrophobic organic compounds in soil pore water. Laboratory tests assess the device's hydraulic performance and capture efficiency for chlorinated aromatics. The role of separate phase oil containing PCBs is modeled to evaluate the release of PCBs from hydraulic oils in sediment and soil (Sean McNamara).

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Contaminant Control Technology
Toxic Trace Metal Removal Processes - Leckie, J. O. (WRHSRC, EPA) General project objectives are to study the adsorption/desorption characteristics of toxic metals and metalloids, including radionuclides as well as stable isotopes, under conditions where competing organic ligands are present and where remobilization might occur (e.g., contaminated ground water systems, mixed industrial wastes). The investigation will focus on several of the following: Cd, Ni, Pb, Cr, Cu, Co, As, and/or Se. The selection of organic ligands will include commercially used sequestering agents (e.g., EDTA) as well as metabolic products from microbial degradation of organic matter. Major experimental variables are pH, temperature, type and concentration of solid, organic ligand and ionic strength. In addition, the fundamental aspects of adsorption reactions of trace metal ions within the pores of porous particles will be studied. This aspect of the study will focus on cases where overall rate of adsorption is limited by internal mass transport constraints. Part of the intent in studying the internal mass transport limited adsorption is to define the chemical and physical limitations of the adsorption process as a function of pore size distribution and to describe the observed phenomena in a mathematical format.

In Situ Anaerobic Bioremediation of Fuel Contaminated Ground Water
- Reinhard, M. (Office of Naval Research).
Ground water contaminated with fuel is typically anaerobic. Under these conditions, microorganisms will use alternate electron acceptors in the order nitrate, sulfate, and carbon dioxide to degrade petroleum derived contaminants. This project aims to demonstrate and evaluate the efficacy of in situ bioremediation that relies on the addition of low doses of alternate electron acceptors. The approach is to amend a contaminated zone of an anaerobic gasoline plume with mixtures of alternate electron acceptors and to observe the enhanced removal of hydrocarbon contaminants. The data will be used to demonstrate the technical viability of anaerobic bioremediation approaches.

Palladium Catalyzed Reduction of Water Contaminants Under Environmental Conditions - Reinhard, M. (EPA).
Many halogenated hydrocarbon compounds are rapidly dehalogenated by hydrogen gas in the presence of a heterogeneous metal catalyst. In addition, catalyzed hydrogenation rapidly reduces some inorganic oxyanions such as nitrate to less toxic forms. The objective of this project to establish the mechanistic basis for designing metal catalyzed detoxification processes. The reactions that occur during simulated treatment at the catalyst surface are investigated using kinetic and surface analytical methods.

Reductive Transformation of Chlorinated Ethenes Catalyzed by Vitamin B12 - Reinhard, M. (WRHSRC).
Transition-metal coenzymes such as vitamin B12 have been implicated as the responsible agents in the respiratory of cometabolic dehalogenation of chlorinated hydrocarbon compounds. Potential biological dehalogenation pathways have been derived from studies in abiotic systems in which catalytic amounts of Ti(III) were used as the bulk reductant. The overall objective of the project is to improve our understanding of the chemistry of B12 mediated dehalogenation reactions. The kinetics of trichloroethylene (TCE) dehalogenation is being studied in abiotic model systems with Ti(III) as the reductant and B12 as the catalyst. The results obtained in abiotic systems are compared with results obtained in biological systems.

Heavy Metals Incorporation into Ceramic Crystalline Matrix - Leckie, J. O. (EPA) The objective of this project is the illucidation of the physical-chemical processes by which selected heavy metals (Pb, Cr, Cu, Co, Cd) are incorporated into the ceramic matrix during firing of clay/metal bearing sludge mixtures. Details of the bonding and location of metals in the ceramic crystalline matrix will be studied using XRD, EXAFS, XPS and SEM. Additional spectroscopic tools include NMR and FTIR. The major experimental variables are type of metal, metal /clay ratio, time and temperature of firing process.

In Situ Treatment of Chlorinated Solvents - McCarty, P. L. (DuPont Chemicals, WRHSRC, EPA, DOE)
Several species of bacteria have been isolated and identified by others that have the ability to reductively dehalogenate chlorinated aliphatic hydrocarbons (CAHs). However, an individual or group of organisms responsible for the complete dehalogenation process from tetrachloroethylene (PCE) to ethene has not yet been identified. The objectives of this study are to describe the bacterium or groups of bacteria that are responsible for conversion of tetrachloroethene (PCE) to ethene in aquifer samples taken from a contaminated site in Victoria, Texas, and to examine the factors affecting the rate and extent of transformation.

Mechanisms, Chemistry, and Kinetics of Anaerobic Biodegradation of cDCE and VC - McCarty, P.L. and Spormann, A.M. (U.S. DOE and DuPont Chemicals)
Biological reductive dehalogenation of the chlorinated ethenes, tetrachloroethene (PCE) and trichloroethene (TCE) to cis-1,2-dichloroethene (cDCE), vinyl chloride (VC) and then ethene is of great interest both for natural attenuation and engineered remediation of these hazardous contaminants in groundwater. This study was directed towards a better understanding of the factors affecting the rate and extent of conversions of cDCE and VC to ethene, which are generally considered the rate limiting steps in the overall process. The objectives of this study are to (1) determine the biochemical pathways for reductive dehalogenation of cDCE and VC, including identification of the enzymes involved, (2) determine the chemical requirements, especially the type and quantity of electron donors needed by the microorganisms for reductive dehalogenation, and (3) evaluate the kinetics of the process with respect to the concentration of both the electron donors and the electron acceptors (cDCE and VC).

Hydrodynamic and Biological Factors Affecting Aquifer Clogging During In-Situ Bioremediation - McCarty, P. L. (WRHSRC, EPA) With in-situ bioremediation processes, bacteria are stimulated to grow on substrates introduced into groundwater. When this is done, there is a potential for clogging of the aquifer by excessive bacterial growth, thus restricting the movement of groundwater and making it difficult to introduced additional chemicals. The object of this study is to learn better how clogging of aquifers occurs, and what characteristics of the aquifer, the chemicals introduced, and microorganisms contribute most to the clogging problem. In order to study these factors, a laboratory investigation is being conducted in which enhanced imaging is used to better evaluate the hydrodynamic and biological factors involved.

Field Demonstration of Vertical and Horizontal Recirculation Wells for In Situ Treatment of Chlorinated Solvent Contaminated Groundwater - Mark N. Goltz, Perry L. McCarty, Steve M. Gorelick, and Gary Hopkins. (Strategic Environmental Research and Development Program) The purpose of this study is to evaluate the potential for removal of chlorinated organic solvents at their source in an aquifer by combining two processes, in-well vapor stripping and in situ aerobic cometabolic biodegradation. The combined system is termed BioEnHanced In Well Vapor Stripping (BEHIVS). The system will be evaluated at full scale in the field at a trichloroethylene (TCE) contaminant groundwater site at Edwards Air Force Base.

Development of Effective Aerobic Cometabolic Systems for the In-situ Transformation of Problematic Chlorinated Solvent Mixtures - Lewis Semprini, Daniel Arp, Perry L. McCarty, and Gary Hopkins (Strategic Environmental Research and Development Program) The goal of the proposed research is to demonstrate the potential of using propane and butane-utilizing microorganisms to transform problematic chlorinated solvent (CAH) mixtures in groundwater. The demonstration at the Moffett Federal Airfield Test Site will be aimed towards recirculation well treatment systems that can be used to create bioreactive passive barriers in contaminated aquifers. Our research with microorganisms stimulated on propane or butane has demonstrated the potential for transforming a broad range of CAH mixtures that have been problematic with other cometabolic substrates. Microcosm studies conducted with subsurface solids and groundwater from contaminated DOD sites, however, have shown that propane and butane-utilizers are often absent in the subsurface, or have long lag periods before effective stimulation is acheived. The proposed work will demonstrate effective methods to create passive treatment barriers through both bioaugmentation and the use of recirculation well technology. Microbial growth and maintenance for effective cometabolic treatment will be achieved through propane or butane addition to the subsurface. In addition, we will explore the use of mixed cometabolic substrates for the treatment of problematic CAH mixtures.

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Environmental Planning and Management

The following is a current list of projects that are being either undertaken or supervised by Leonard Ortolano, UPS Foundation Professor of Civil Engineering. Several of these projects are being undertaken by Ph. D. students in the Interdisciplinary Program on Environment and Resources ( http://iper.stanford.edu ) and by Professor Ortolano with recent Stanford Ph D graduates

Policy-Level Strategic Environmental Assessments: Lessons from Case Studies and National Program Evaluations
Interest in the application of environmental assessment procedures to policy proposals is growing. Six case studies and two national program evaluations are analyzed to identify lessons that can be drawn about the state of the practice of policy-level strategic environmental assessment (SEA). The analysis shows that SEA's influence on policy outcomes depends heavily on how assessments are integrated into policy design. Based on the case studies, a typology consisting of four modes of integration is presented. For some (but not all) approaches to integration, SEAs can be an effective mechanism for enhancing inter-agency coordination and public involvement in policy making and for integrating environmental considerations into policy design. The national evaluations show that, in many instances, ministries required to prepare SEAs on proposed policies do so in a pro forma fashion, and the SEAs do not significantly influence policy outcomes. Strategies are proposed for augmenting existing incentives so that the full potential of policy-level SEA can be realized.

Implementing French Policies to Regulate Agricultural Pollution of Groundwater
The design and implementation of regulations to control groundwater pollution from agriculture is a subject of considerable significance throughout the world. There is considerable interest in the French approach to this regulatory issue because of the existence of water management institutions linked to France's six water agencies). These agencies, which cover all of continental France, have a unique approach to integrating stakeholder participation in the creation of basin-wide water management plans. The agencies also have economic tools - in the form of water fees, effluent charges and subsidy programs - that influence plan implementation. This research investigates the strategies used by these agencies to assist in regulating groundwater pollution from agriculture, such as pollution of aquifers with nitrogen from feedlots. The approaches taken by the French water agencies must be consistent with both applicable European Union directives and the complex inter-ministerial arrangements for enforcing environmental rules that existed before the agencies were created. This research identifies characteristics of the French strategy for controlling pollution from agriculture are successful, and it aims to identify general lessons that can be learned from the French experience.   

Influence of a Water Rights Markets on Settlements of Environmental Disputes in New Mexico
After decades of contention, several long-standing water disputes in New Mexico have reached the stage of settlement without relying on the State's complex and time-consuming process for adjudicating water rights. These conflicts involve diverse groups including Native American tribes with sovereign nation status, irrigation-based acequia communities where water rights descend from Spanish land grants, irrigation districts and other farmers and ranchers, residential well owners, urban and industrial water users and environmental interests. In attempting to untangle the factors that have encouraged this relatively sudden movement toward settlements, this research focuses on the influence of emerging markets in water rights. The linkages between the rights markets and settlements exist because settlements allow senior rights holders to legally define their rights and thereby make them both enforceable and marketable. Junior rights holders, fearing that they may lose the water they currently are able to access, welcome the settlements because they can purchase water rights on the market. This research is being done with the collaboration of Sandia National Laboratory and with the cooperation of several offices of the New Mexico state government.

Cooperatives, Social Networks and the Supply of Water to the Poor in Argentina
In many parts of Argentina, the poor have gained access to drinking water by organizing themselves into cooperatives, voluntary membership organizations that are democratic and member controlled, and that have a "double bottom line": they must remain financially sustainable and deliver water to all their members, including the poor. These two goals are sometimes in conflict. This research investigates propositions concerning how social networks among members of cooperatives, and affiliations between leaders of cooperatives and local elites, affect the ability of cooperatives to meet their dual goals. The research includes a survey of all cooperatives delivering water supply services in Argentina as well as in-depth case studies of water cooperatives operating in the peri-urban areas of Buenos Aires.  

Organizational Learning in Small Community Water Providers in California 
This research, which aims to better understand how rural water supply infrastructure can provide reliable and safe drinking water supply in a sustainable fashion, focuses on how small community water providers learn to solve problems and adapt to changing circumstances. Organizational learning in small community water providers is conceptualized in a way that recognizes ways in which small water providers in California interpret their external environments, and the research considers the capacity of these organizations to respond to exogenous institutional factors. A comparative case study analysis is being conducted of several small community water providers in California.   Results from this research will contribute to organizational learning theory as well as to the development of innovative learning tools for small water systems.

Contentious Politics in Liquefied Natural Gas Facility Siting in California
The siting of locally unwanted land uses (LULUs) - for example, hazardous waste facilities, landfills, prisons, and power plants - continues to be a challenging task. The goal of this research is to better comprehend the context and factors that spark local community mobilization and to understand mobilization processes in the context of LULUs. Efforts to site Liquefied Natural Gas facilities in California provide a basis for studying community mobilization processes in detail. A number of hypotheses - drawn from the facility siting, public participation and social movements literatures - related to community mobilization around LULU siting proposals can be derived. Use of a comparative case study methodology allows for the continual refinement of hypotheses while gathering new information in the different contexts surrounding each case.

Effects of China's Legal System on Enforcement of Environmental Regulations
Increasingly, polluters facing environmental penalties in China are relying on laws that allow them to challenge the government's regulatory decisions in court. Plaintiffs in these cases can prevail if they are able to demonstrate that regulators erred in imposing penalties. Research at municipalities in Hubei Province is investigating whether and how these legal actions by polluters have affected both the organizational structures and administrative procedures used by local environmental protection bureaus. The focus is an enforcement procedures used by these bureaus. Qualitative aspects of the research rely on a multiple case study designs where each case relies on legal documentation as well as interviews with lawyers, judges, plaintiffs and environmental officials among others. Quantitative data based on archival court records is also compiled and analyzed. The research is being conducted in collaboration with the Environmental and Resource Law Research Center of the Zhongnan University of Economics and Law in Wuhan.

Adoption and Implementation of Vehicle Emission Standards in Chinese Cities
Automobile ownership in China has grown rapidly since the 1980s, and many large cities have experienced serious air pollution problems due to releases from automobile tailpipes. Since the mid 1990s, automobiles have become the primary source of urban air pollution in China. To tackle this problem, in the 1990s governments at both local and national levels began to take strict measures to control emissions from vehicles. Arguably, the most prominent of these measures was the stringent "Euro series" of vehicle emission standards, which refers to a series of European emission standards, such as Euro I, and Euro II. The process of adopting and implementing the Euro series has not been a smooth one. In some cases, national agencies simultaneously issued inconsistent vehicle emissions regulations, and in other cases, the regulations issued were not implementable. This research uses alternative models of organizational decision making to explain inconsistencies and shortfalls in implementation. It also focuses on the implementation of emission control requirements in Beijing and Shanghai. A large data set on emission test results for sections of Beijing is used to investigate whether some motor vehicle models have consistently had difficulties in meeting tailpipe emission standards. This part of the study relies on both descriptive statistics and logit modeling.

Policy Change in Japan: the Tokyo Metropolitan Government's Regulation of Diesel Pollution
For many years, the government of Japan had a fairly relaxed policy towards the regulation of emissions from diesel vehicles. Due in large measure to diesel pollution, air quality in Tokyo declined substantially in the late 1980s and remained poor in the following decade. In 1999, Tokyo took the initiative in modifying diesel emission regulations and made them much more stringent than the national requirements. This research examines reasons for Tokyo's actions and the extent to which these actions caused the national government to change diesel emission regulations for the entire country. The study also investigates how Tokyo's new policy structured the Japanese domestic market for diesel pollution control technologies. In addition, the research employs a quantitative approach to calculate the influence of Tokyo's new policy on total emissions from diesel trucks.



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Environmental Microbiology and Biotechnology

Biochemistry and Genetics of Anaerobic Oxidation of Aromatic Hydrocarbons - Alfred Spormann (NSF)
Oxidation of aromatic hydrocarbons, such as benzene, toluene, ethylbenzene, and xylenes (BTEX) by anaerobic bacteria is of considerable biochemical and environmental interest. The enzymes involved in the initial degradation reactions of these substrates are dramatically different from the well-characterized aerobic oxidation reactions: In all aerobic pathways, the initial reactions involve mono- or dioxygenases that require molecular oxygen as a substrate. Anaerobic bacteria face the biochemical problem of how to perform the first oxidation step in the absence of molecular oxygen.

From an environmental point of view, degradation of these aromatic hydrocarbons is important, because they represent major components of the water soluble fraction of gasoline fuel. Leaking underground fuel storage tanks or surface spills often release these compounds into aquifers. Through research in the recent years, two fundamentally different modes to initiate anaerobic mineralization of alkylbenzenes are emerging: Methyl benzenes are activated by addition of the methyl groyup to fumarate, and benzylsuccinate synthase represents the prototype of this reaction. Alkylbenzenes with side chain lengths of * 2 carbons are anaerobically oxidized at the methylene carbon for which ethylbenzene dehydrogenase serves as the prototype.

One focus of our research is the novel enzyme benzylsuccinate synthase which catalyzes as the initial reaction in anaerobic activation of toluene the addition of the toluene methyl group to fumarate to form benzylsuccinate:
http://www-ce.Stanford.EDU:80/~spormann/Bss%20reaction.JPG

This is a unique non-redox reaction to activate methyl benzenes and also a novel mode to form a new carbon-carbon bond. This enzyme is of considerable interest because it carries an organic free glycyl radical. Biochemical and molecular studies are directed to elucidate the reaction mechanism. A similar reaction is involved in anaerobic activation of m-xylene.

The other focus is on anaerobic ethylbenzene dehydrogenase which catalyzes the first reaction in anaerobic ethylbenzene mineralization. Ethlbenzene dehydrogenase is an unusual enzyme because it catalyzes the oxidation of a hydrocarbon in the absence of molecular oxygen and converts ethylbenzene to 1-phenylethanol with p-benzoquinone as electron acceptor. http://www-ce.Stanford.EDU:80/~spormann/EBreactions.JPG

Biochemical studies are conducted with purified enzymes, and gas chromatography (GC), gas chromatography/ mass spectrometry (GC/MS), HPLC, and spectrophotometry assist in analyzing these unusual reactions.

A parallel genetic approach is directed to identify the structural genes involved and to understand the molecular mechanisms of their control. The current focus of the genetic approach is to generate mutants defective in aromatic hydrocarbon metabolism, and to isolate and to clone the genes involved by genetic complementation.

Anaerobic transformation of chloroethenes and evolution of pathways for transformation of "unnatural" compounds. - Alfred Spormann (SERDP)
Next to the BTEX compounds, chlorinated alkenes, such as tetrachloroethene (PCE), trichloroethene (TCE), dichloroethene (DCE), and vinyl chloride (VC) are another important class of groundwater contaminants in the U.S.. These chlorinated aliphatic compounds are exclusively of anthropogenic origin and have been introduced involuntarily into the environment only within the last decades. Chlorinated aliphatic solvents are frequently used for the degreasing of engines and in dry-cleaning processes. PCE and TCE, but more importantly VC, are highly toxic compounds, and their concentrations in drinking water are regulated. Interestingly, under anaerobic conditions PCE and TCE are metabolized to VC, and, thus, are converted into a product that is more toxic than the parent compound. From a fundamental point of view, the microbial transformation of these compounds is very interesting because these unnatural chemicals were introduced into the environment only a few decades ago. Nevertheless, pathways that metabolize these compounds have evolved in some organisms. Thus, research on these novel microbes that can completely degrade these unnatural compounds allows us to address the more fundamental question of how novel pathways for the degradation of unnatural compounds evolve in nature.
Recently, we discovered a novel mode of anaerobic reductive vinyl chloride transformation to ethylene. Previously known reductive dehalogenation of PCE, TCE, or chlorobenzoates were shown to involve corrinoids as the catalytically active reagent. Through inhibitor studies with cell-free extracts from an anaerobic, VC-dehalogenating mixed culture, we discovered that VC reduction to ethene does not involve a corrinoid. Current, work investigates the microbial and molecular mechanism of this novel enzymatic activity. Understanding the fundamentals of natural dehalogenation of unnatural compounds will provide crucial knowledge that will allow also the development of novel in situ strategies to specifically target biodegradation of VC to this microbial mechanism. Furthermore, understanding this mechanism may also provide tools for engineering a chemical remediation scheme, as has been done using vitamin B12-based chemical reductive dehalogenation of PCE and TCE that was first discovered as a prokaryotic transformation reaction.

In addition, a novel research approach explores the in vitro engineering of enzymes with novel catalytic properties for the transformation of recalcitrant chemicals by use of directed evolution.

Functional Genomics and Physiology of Microbes in Biofilms - Alfred Spormann, Gordon E. Brown, Jr. (NSF)
Microbial biofilms are structures where microbes are attached to a surface and embedded in an extracellular polysaccharide (EPS) matrix. Microbial biofilms form on virtually all aqueous environmental interfaces, including the surfaces of ships, pipes, and sewers, and on soil mineral particles. Biofilms are of enormous economic, medical, and biogeochemical importance. Our work is at the interface of molecular microbiology, molecular microbial ecology, and biogeochemistry.

Biofilms are dynamic structures and undergo a developmental process consisting of (i) initial attachment, (ii) microcolony formation, (iii) maturation, and (iv) detachment. Because cells are constrained in a biofilm and because free diffusion of small molecules is affected within a biofilm, these bioflms exhibit a high degree of internal heterogeneity, where the overall biological activity of a biofilm is controlled by an intricate structure-function relationship. Therefore, individual cells, as well as the overall microbial community, respond to changes in the environment. Thus, the activity of a microbe within a biofilm is a function of its position in the biofilm.

We are studying the cell-cell and cell-substratum intractions using a new genomic approach in conjunction with confocal laser scanning microscopy (CLSM). Our goal is to understand and to predict the complex metabolic and signaling interactions that occur between biofilm microbes. We use two model microbes, Shewanella oneidensis MR-1 and Vibrio cholerae. The genome of both microorganisms has been sequenced, and we are using DNA microarrays to generate profiles of whole cell gene expression during cell-cell and cell-surface interactions. CLSM is a powerful technology to visualize individual microbial cells in biofilms and to visualize the expression of individual genes in biofilm cells. This allows us to observe directly metabolic and signaling cell-cell interactions in active biofilms. This CLSM work is conducted here at the new Stanford Biofilm Research Center.

S. oneidensisutilizes the surface of insoluble Fe(III) minerals as electron acceptor and forms biofilms on such minerals. The reduced Fe(II) minerals, in turn, are critically important for geochemical redox reactions involved in abiotic heavy metal mobilization and reductive degradation reactions. We are specifically interested in the molecular processes that control S. oneidensis biofilm formation and stability, and that are involved in redox reactions between biofilm cells and the mineral subtratum.

V. cholerae forms biofilms on inorganic and organic, including chitin, surfaces. It is believed that chitin provides a critical metabolizable substrate for this microbe to persistent in marine environments. Also here, we are using a genomic approach to uncover cell-cell and cell-substratum interactions of V. cholerae in marine environments and on chitin surfaces.

This project is part of an interdisciplinary NSF-funded research effort (CREAMS) on "Chemical and Microbial Interactions on Environmental Surfaces"

Reductive processes for the bioremediation of chlorinated solvent metal mixtures - Craig Criddle, Alfred Spormann (NIEHS).
Mixtures of chlorinated solvenets and metals pose a significant challenge for bioremediation. This work focuses on the transfer of the the carbon tetrachloride degradation genes encoding production of pyridine-2,6-bis(thiocarboxylate) (PDTC) from Pseudomonas stutzeri strain KC to Shewanella oneidensis MR1 to create an organism with increased metal tolerance and the ability to dechlorinate carbon tetrachloride.

Field-scale evaluation of biostimulation for remediation of uranium-contaminated groundwater - Craig Criddle, Peter Kitanidis, and Gary Hopkins (U.S. DOE).
Microbial reduction of uranium may prevent its migration to receptor streams. However, application of this technology to field sites is untested, and future site remediation will require improved understanding of basic processes and implementation strategies in heterogeneous environments. The goals of this work are (1) to develop a predictive capability for the rates and mechanisms controlling microbial reduction of U in heterogeneous field settings, and (2) to develop a system capable of delivering electron donor to a highly heterogeneous subsurface environment enabling spatially uniform in situ immobilization of U in groundwater upon passage through a subsurface biocurtain. This work involves a 3-phase field study in a near surface aquifer at Oak Ridge, TN. This aquifer contains very high levels of nitrate and part per million levels of U(VI). The nitrate must be removed because it prevents reduction of U, and, if the nitrate is reduced to N2 the resulting gas could reduce aquifer permeability. We will test in-situ concepts for nitrate removal: an in-well vacuum stripper; an in-well bioreactor; and ion selective resins. The most effective and least expensive system will be coupled to a system for in-situ uranium removal. By removing the nitrate, we will be able to impose hydrological and geochemical controls on the U source permitting reliable determination of U reduction rates within a downgradient biocurtain for U immobilization. We plan to use field-scale and companion bench-scale studies to evaluate hypotheses on dissimilatory metal-reducing activity, and we will be monitoring changes in microbial community dynamics using molecular methods.

Proof of gene expression during bioaugmentation - Craig Criddle (WRHSRC, EPA)
Experimental justification for bioaugmentation is typically obtained by comparing the bioremediation of inoculated and uninoculated samples. This approach is adequate for bench-scale studies. At full scale, however, design and operation of uninoculated controls is difficult and expensive. Inadvertent inoculation of "uninoculated" regions must be avoided, and the inoculated and uninoculated regions must initially be geologically, chemically, and biologically similar. Other methods, besides the use of uninoculated control regions, are needed to establish that added organisms are in fact mediating the desired transformations. A logical approach is to prove expression of the genes required for the desired transformation. Gene expression occurs at different levels as the synthesis of mRNA (transcription), the formation of polypeptides (translation), and the biochemical reaction itself. Proof of gene expression is best obtained at each level, because each piece of evidence strengthens the conclusion that gene expression is occurring as intended. This proposal explores each level of gene expression for the bioremediation of carbon tetrachloride by Pseudomonas stutzeri KC.

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