Concurrent bioremediation of perchlorate and 1,1,1-trichloroethane in an emulsified oil barrier

A detailed field pilot test was conducted to evaluate the use of edible oil emulsions for enhanced in situ biodegradation of perchlorate and chlorinated solvents in groundwater. Edible oil substrate (EOS) was injected into a line of ten direct push injection wells over a 2-day period to form a 15-m-long biologically active permeable reactive barrier (bio-barrier). Field monitoring results over a 2.5-year period indicate the oil injection generated strongly reducing conditions in the oil-treated zone with depletion of dissolved oxygen, nitrate, and sulfate, and increases in dissolved iron, manganese and methane. Perchlorate was degraded from 3100 to 20,000 microg/L to below detection (<4 microg/L) in the injection and nearby monitor wells within 5 days following the injection. Two years after the single emulsion injection, perchlorate was less than 6 microg/L in every downgradient well compared to an average upgradient concentration of 13,100 microg/L. Immediately after emulsion injection, there were large shifts in concentrations of chlorinated solvents and degradation products due to injection of clean water, sorption to the oil and adaptation of the in situ microbial community. Approximately 4 months after emulsion injection, concentrations of 1,1,1-trichloroethane (TCA), perchloroethene (PCE), trichloroethene (TCE) and their degradation products appeared to reach a quasi steady-state condition. During the period from 4 to 18 months, TCA was reduced from 30-70 microM to 0.2-4 microM during passage through the bio-barrier. However, 1-9 microM 1,1-dichloroethane (DCA) and 8-14 microM of chloroethane (CA) remained indicating significant amounts of incompletely degraded TCA were discharging from the oil-treated zone. During this same period, PCE and TCE were reduced with concurrent production of 1,2-cis-dichloroethene (cis-DCE). However, very little VC or ethene was produced indicating reductive dechlorination slowed or stopped at cis-DCE. The incomplete removal of TCA, PCE and TCE is likely associated with the short (5-20 days) hydraulic retention time of contaminants in the oil-treated zone. The permeability of the injection wells declined by 39-91% (average=68%) presumably due to biomass growth and/or gas production. However, non-reactive tracer tests and detailed monitoring of the perchlorate plume demonstrated that the permeability loss did not result in excessive flow bypassing around the bio-barrier. Contaminant transport and degradation within the bio-barrier was simulated using an advection-dispersion-reaction model where biodegradation rate was assumed to be linearly proportional to the residual oil concentration (Soil) and the contaminant concentration. Using this approach, the calibrated model was able to closely match the observed contaminant distribution. The calibrated model was then used to design a full-scale barrier to treat both ClO4 and chlorinated solvents.     

Enhanced reductive dechlorination in columns treated with edible oil emulsion

The effect of edible oil emulsion treatment on enhanced reductive dechlorination was evaluated in a 14 month laboratory column study. Experimental treatments included: (1) emulsified soybean oil and dilute HCl to inhibit biological activity; (2) emulsified oil only; (3) emulsified oil and anaerobic digester sludge; and (4) continuously feeding soluble substrate. A single application of emulsified oil was effective in generating strongly reducing, anaerobic conditions for over 14 months. PCE was rapidly reduced to cis-DCE in all three live columns. Bioaugmentation with a halorespiring enrichment culture resulted in complete dechlorination of PCE to ethene in the soluble substrate column (yeast extract and lactate). However, an additional treatment with a pulse of yeast extract and bioaugmentation culture was required to stimulate complete dechlorination in the emulsion treated columns. Once the dechlorinating population was established, the emulsion only column degraded PCE from 90-120 microM to below detection with concurrent ethene production in a 33 day contact time. The lower biodegradation rates in the emulsion treated columns compared to the soluble substrate column suggest that emulsified oil barriers may require a somewhat longer contact time for effective treatment. In the HCl inhibited column, partitioning of PCE to the retained oil substantially delayed PCE breakthrough. However, reduction of PCE to more soluble degradation products (cis-DCE, VC and ethene) greatly reduced the impact of oil-water partitioning in live columns. There was only a small decline in the hydraulic conductivity (K) of column #1 (low pH+emulsion, K(final)/K(initial)=0.57) and column #2 (live+emulsion, K(final)/K(initial)=0.73) indicating emulsion injection did not result in appreciable clogging of the clayey sand. However, K loss was greater in column #3 (sludge+emulsion, K(final)/K(initial)=0.12) and column #4 (soluble substrate, K(final)/K(initial)=0.03) indicating clogging due to biomass and/or gas production can be significant.     

Impact of edible oil injection on the permeability of aquifer sands

Recent laboratory and field studies have shown that food-grade edible oils can be injected into the subsurface for installation of in-situ permeable reactive barriers. However to be effective, the oil must be distributed out away from the oil injection points without excessive permeability loss. In this work, we examine the distribution of soybean oil in representative aquifer sediments as non-aqueous phase liquid oil (NAPL oil) or as an oil-in-water emulsion. Laboratory columns packed with sands or clayey sands were flushed with either NAPL oil or a soybean emulsion followed by plain water, while monitoring permeability loss and the final oil residual saturation. NAPL oil can be injected into coarse-grained sands. However NAPL injection into finer grained sediments requires high injection pressures which may not be feasible at some sites. In addition, NAPL injection results in high oil residual saturations and moderate permeability losses. In contrast, properly prepared emulsions can be distributed through sands with varying clay content without excessive pressure buildup, low oil retention and very low to moderate permeability loss. For effective transport, the emulsion must be stable, the oil droplets must be significantly smaller than the mean pore size of the sediment and the oil droplets should have a low to moderate tendency to stick to each other and the aquifer sediments. In our work, oil retention and associated permeability loss increased with sediment clay content and with the ratio of droplet size to pore size. For sandy sediments, the permeability loss is modest (0-40% loss) and is proportional to the oil residual saturation.     

Modeling field-scale multiple tracer injection at a low-level waste disposal site in fractured rocks: effect of multiscale heterogeneity and source term uncertainty on conceptual understanding of mass transfer processes

Multiple factors may affect the scale-up of laboratory multi-tracer injection into structured porous media to the field. Under transient flow conditions and with multiscale heterogeneities in the field, previous attempts to scale-up laboratory experiments have not answered definitely the questions about the governing mechanisms and the spatial extent of the influence of small-scale mass transfer processes such as matrix diffusion. The objective of this research is to investigate the effects of multiscale heterogeneity, mechanistic and site model conceptualization, and source term density effect on elucidating and interpreting tracer movement in the field. Tracer release and monitoring information previously obtained in a field campaign of multiple, conservative tracer injection under natural hydraulic gradients at a low-level waste disposal site in eastern Tennessee, United States, is used for the research. A suite of two-pore-domain, or fracture-matrix, groundwater flow and transport models are calibrated and used to conduct model parameter and prediction uncertainty analyses. These efforts are facilitated by a novel nested Latin-hypercube sampling technique. Our results verify, at field scale, a multiple-pore-domain, multiscale mechanistic conceptual model that was used previously to interpret only laboratory observations. The results also suggest that, integrated over the entire field site, mass flux rates attributable to small-scale mass transfer are comparable to that of field-scale solute transport. The uncertainty analyses show that fracture spacing is the most important model parameter and model prediction uncertainty is relatively higher at the interface between the preferred flow path and its parent bedrock. The comparisons of site conceptual models indicate that the effect of matrix diffusion may be confined to the immediate neighborhood of the preferential flow path. Finally, because the relatively large amount of tracer needed for field studies, it is likely that source term density effect may exaggerate or obscure the effect of matrix diffusion on the movement of tracers from the preferred flow path into the bedrock.     

Injection of innocuous oils to create reactive barriers for bioremediation: laboratory studies

In situ groundwater remediation may be achieved using stationary permeable barriers created by the injection of a substrate, such as innocuous vegetable oil, into the contaminated aquifer. The oil provides the electron donor stimulating microorganisms to degrade or sequester many contaminants. At present, little is known about the best procedures to use when injecting oil into an aquifer. In this investigation, laboratory column and sand tank studies were used as model systems to explore the effect of different injection parameters on the distribution of oil emulsions into water-saturated sand. The parameters investigated included injection pressures of 70, 1400 and 18,000 KPa; injection times of 15, 30, 60 or 120 s; and the influence of an emulsifier, polyoxyethylenesorbitan monooleate (Tween 80), upon the distribution of the injected oil. The longest injection patterns were achieved at 18,000 KPa. A pattern that was 46+/-1.8 cm long was produced with an 18,000 KPa injection for 60 s. Increasing the injection time to 120 s increased the length of the pattern by only 6.5%. Tween 80 at concentrations of 0.05% increased the width of the injection patterns but did not increase the length of the pattern. A multi-ported injection probe might be used to create in situ permeable barriers approximately 1 m wide.     

Hydraulic characterization for steam enhanced remediation conducted in fractured rock

To explore the viability of Steam Enhanced Remediation (SER) in fractured rock a small-scale steam injection and water/vapour extraction pilot study was conducted at the former Loring Air Force Base in northern Maine, USA. A detailed well testing program was undertaken to assist in the design of the injection and extraction well array, and to assess the possibility of off-site heat and contaminant migration. A structurally complex limestone having low matrix porosity and a sparse distribution of fractures underlies the study site. To characterize the groundwater and steam flow pathways, single-well slug tests and more than 100 pulse interference tests were conducted. The results of the well testing indicate that the study site is dominated by steeply dipping bedding plane fractures that are interconnected only between some wells in the injection/extraction array. The SER system was designed to take advantage of interconnected fractures located at depth in the eastern end of the site. An array of 29 wells located in an area of 60 by 40 m was used for steam injection and water/vapour extraction. The migration of heat was monitored in several wells using thermistor arrays having a 1.5 m vertical spacing. Temperature measurements obtained during and after the 3 month steam injection period showed that heat migration generally occurred along those fracture features identified by the pulse interference testing. Based on these results, it is concluded that the pulse interference tests were valuable in assisting with the design of the injection/extraction well geometry and in predicting the migration pathways of the hot water associated with the steam injection. The pulse interference test method should also prove useful in support of any other remedial method dependant on the fracture network for delivery of remedial fluid or extraction of contaminants.     

Optimization and treatment of wastewater of crude oil desalting unit and prediction of scale formation

In this article, one of Iran’s southwest oil fields that produces 3200 barrels per day (bbl/d) of wastewater from oil and gas processing was investigated. Experimental analysis of oil reservoir water and desalting wastewater disposal of crude oil desalting unit was performed. First, water was treated with a reverse osmosis membrane. As a result, the purified water, with lower total dissolved solids (TDS) and pH, was a suitable candidate for injection into the adjacent wells of the crude oil desalting unit. The effectiveness and compatibility of this wastewater to the formation water of the oil field wells were simulated. Finally, we studied and identified the formation, the amount, and the type of mineral scale deposits. These are the most important problems during water injection into the wells. The analysis shows that the refined water from the reverse osmosis (RO) process was a suitable and low-cost economical option for injection in onshore and offshore fields, due to the low amount of salts, the concentration of susceptible ions in scaling formation, and the appropriate pH. This oil field, which is in the second half of life, requires enhanced oil recovery methods (EOR) for the maintenance of pressure and an increase in oil recovery.

     

A parametric transfer function methodology for analyzing reactive transport in nonuniform flow

We analyze reactive transport during in-situ bioremediation in a nonuniform flow field, involving multiple extraction and injection wells, by the method of transfer functions. Gamma distributions are used as parametric models of the transfer functions. Apparent parameters of classical transport models may be estimated from those of the gamma distributions by matching temporal moments. We demonstrate the method by application to measured data taken at a field experiment on bioremediation conducted in a multiple-well system in Oak Ridge, TN. Breakthrough curves (BTCs) of a conservative tracer (bromide) and a reactive compound (ethanol) are measured at multi-level sampling (MLS) wells and in extraction wells. The BTCs of both compounds are jointly analyzed to estimate the first-order degradation rate of ethanol. To quantify the tracer loss, we compare the approaches of using a scaling factor and a first-order decay term. Results show that by including a scaling factor both gamma distributions and inverse-Gaussian distributions (transfer functions according to the advection-dispersion equation) are suitable to approximate the transfer functions and estimate the reactive rate coefficients for both MLS and extraction wells. However, using a first-order decay term for tracer loss fails to describe the BTCs at the extraction well, which is affected by the nonuniform distribution of travel paths.     

Movement and degradation of aldicarb residues in the saturated zone under citrus groves on the Florida ridge

A 1.7-ha section of citrus grove near Lake Hamilton was the site of a three-year field study designed to monitor the movement and degradation of the nematicide and insecticide aldicarb in the central ridge area of Florida. Soil cores were used to monitor the fate of aldicarb residues in the unsaturated zone and over 2,000 groundwater samples were collected from 174 monitoring wells to measure horizontal and vertical transport of aldicarb residues in the saturated zone. A simple saturated zone model was used to estimate the degradation rate of aldicarb residues and extrapolate findings to other ridge areas.The results of the study suggest that in the saturated zone aldicarb residues degrade at a rate corresponding to a half-life of approximately eight months. The predominantly horizontal movement of groundwater at this site limits aldicarb residues to the upper three to five meters of the saturated zone. Field data from this site together with unsaturated and saturated zone simulations suggest that in this area of Florida current restrictions on aldicarb used near potable wells are adequate to protect drinking water supplies.     

Development of a fuzzy-stochastic nonlinear model to incorporate aleatoric and epistemic uncertainty

Site uncertainties significantly influence groundwater flow and contaminant transport predictions. Aleatoric and epistemic uncertainty are both identified in site characterization and represented using proper uncertainty theories. When one theory best represents one parameter whereas a different theory may be more suitable for another parameter, the hybrid propagation of aleatoric (random) and epistemic (nonrandom) uncertainties will occur. The computational challenges of joint propagation of aleatoric and epistemic uncertainty through groundwater flow and contaminant transport models are significant. A fuzzy-stochastic nonlinear model was developed in this paper to incorporate these two types of uncertain site information and reduce the computational cost. The results show that (1) the computational cost using the nonlinear model is reduced compared with that of using the sparse grid algorithm and Monte Carlo methods; (2) the uncertainty of hydraulic conductivity (K) significantly influences the water head and solute distribution at the observation wells compared to other uncertain parameters, such as the storage coefficient and the distribution coefficient (K_d); and (3) the combination of multiple uncertain parameters substantially affects the simulation results. Neglecting site uncertainties may lead to unrealistic predictions.     

Importance of considering intraborehole flow in solute transport modeling under highly dynamic flow conditions

Correct interpretation of tracer test data is critical for understanding transport processes in the subsurface. This task can be greatly complicated by the presence of intraborehole flows in a highly dynamic flow environment. At a new tracer test site (Hanford IFRC) a dynamic flow field created by changes in the stage of the adjacent Columbia River, coupled with a heterogeneous hydraulic conductivity distribution, leads to considerable variations in vertical hydraulic gradients. These variations, in turn, create intraborehole flows in fully-screened (6.5m) observation wells with frequently alternating upward and downward movement. This phenomenon, in conjunction with a highly permeable aquifer formation and small horizontal hydraulic gradients, makes modeling analysis and model calibration a formidable challenge. Groundwater head data alone were insufficient to define the flow model boundary conditions, and the movement of the tracer was highly sensitive to the dynamics of the flow field. This study shows that model calibration can be significantly improved by explicitly considering (a) dynamic flow model boundary conditions and (b) intraborehole flow. The findings from this study underscore the difficulties in interpreting tracer tests and understanding solute transport under highly dynamic flow conditions.     

Modeling field-scale cosolvent flooding for DNAPL source zone remediation

A three-dimensional, compositional, multiphase flow simulator was used to model a field-scale test of DNAPL removal by cosolvent flooding. The DNAPL at this site was tetrachloroethylene (PCE), and the flooding solution was an ethanol/water mixture, with up to 95% ethanol. The numerical model, UTCHEM accounts for the equilibrium phase behavior and multiphase flow of a ternary ethanol-PCE-water system. Simulations of enhanced cosolvent flooding using a kinetic interphase mass transfer approach show that when a very high concentration of alcohol is injected, the DNAPL/water/alcohol mixture forms a single phase and local mass transfer limitations become irrelevant. The field simulations were carried out in three steps. At the first level, a simple uncalibrated layered model is developed. This model is capable of roughly reproducing the production well concentrations of alcohol, but not of PCE. A more refined (but uncalibrated) permeability model is able to accurately simulate the breakthrough concentrations of injected alcohol from the production wells, but is unable to accurately predict the PCE removal. The final model uses a calibration of the initial PCE distribution to get good matches with the PCE effluent curves from the extraction wells. It is evident that the effectiveness of DNAPL source zone remediation is mainly affected by characteristics of the spatial heterogeneity of porous media and the variable (and unknown) DNAPL distribution. The inherent uncertainty in the DNAPL distribution at real field sites means that some form of calibration of the initial contaminant distribution will almost always be required to match contaminant effluent breakthrough curves.     

A case study for demonstrating the application of U.S. EPA's monitored natural attenuation screening protocol at a hazardous waste site

Natural attenuation assessment data, collected at a Superfund site located in Louisiana, USA, are presented. The study site is contaminated with large quantities of DNAPL waste products. Source characterization data indicated that chlorinated ethene and ethane compounds are the major contaminants of concern. This case study illustrates the steps involved in implementing the U.S. EPA's [U.S. EPA, 1998. Technical protocol for evaluating natural attenuation of chlorinated solvents in ground water, by Wiedmeier, T.H., Swnason, M.A., Moutoux, D.E., Gordon, E.K., Wilson, J.T., Wilson, B.H., Kampbell, D.H., Hass, P.E., Miller, R.N., Hansen, J. E., Chapelle, F.H., Office of Research and Development, EPA/600/R-98/128] monitored natural attenuation (MNA) screening protocol at this chlorinated solvent site. In the first stage of the MNA assessment process, the field data collected from four monitoring wells located in different parts of the plume were used to complete a biodegradation scoring analysis recommended by the protocol. The analysis indicates that the site has the potential for natural attenuation. In the second stage, a detailed conceptual model was developed to identify various contaminant transport pathways and exposure points. The U.S. EPA model and BIOCHLOR was used to assess whether the contaminants are attenuating at a reasonable rate along these transport paths so that MNA can be considered as a feasible remedial option for the site. The site data along with the modeling results indicate that the chlorinated ethene and chlorinated ethane plumes are degrading and will attenuate within 1000 ft down gradient from the source, well before reaching the identified exposure point Therefore, MNA can be considered as one of the feasible remediation options for the site.     

Field test of a cross-injection scheme for stimulating in situ denitrification near a municipal water supply well

A pilot-scale test of an in situ denitrification scheme was undertaken to assess an adaptation of the nutrient injection wall (NIW) technology for treating a deep (30-40 m) nitrate contamination problem (N-NO(-)(3) ~ 10-12 mg/L). The adaptation is called the Cross-Injection Scheme (CIS). It duplicates the NIW method without a wall; wells are installed and operated directly in the aquifer and high-flux zones of the aquifer are preferentially targeted for treatment. The test was conducted on the site of a municipal water supply well field, with the supply well pumping between 15-80 m(3)/h. Acetate was periodically injected into the aquifer between an injection-extraction well pair positioned across the normal direction of flow. The injected pulses were then permitted to move with the water toward the municipal wells, providing a carbon supply to drive the desired denitrification. The fate of nitrate, nitrite, acetate and sulphate were monitored at multilevel wells located between the injection location and the municipal wells. The acetate pulsing interval was approximately weekly (9 h injections), so that the system was operating passively 95% of the time. Previous work on the site has established that the highest solute fluxes were associated with a 1-3 m thick zone about 35 m below surface. This zone was found to respond to the acetate additions as a function of the municipal pumping rate and the carbon-to-nitrogen ratio (i.e., determined by the injected acetate concentration). Initially, acetate was injected just below the theoretical stoichiometric requirement for complete denitrification and nitrate disappearance was accompanied by nitrite production. Increasing the C:N ratio (doubling the acetate injection concentration) increased the removal of nitrate and diminished the occurrence of nitrite. Slowing the municipal pumping rate, with a C:N ratio of 1.2-1.6, resulted in complete nitrate attenuation with no nitrite production and no sulfate reduction. The experiment demonstrated that the CIS injection scheme is a viable option for the treatment of nitrate contamination in situ near high-capacity wells.     

Plutonium in groundwater at the 100K-Area of the U.S. DOE Hanford Site

We examined the concentration, size distribution, redox state and isotopic composition of plutonium (Pu) in groundwater at the 100K-Area at the U.S. Department of Energy's (DOE) Hanford Site. Total concentrations of Pu isotopes were extremely low (10(-4) to 10(-6) pCi/kg, approximately 10(4) to 10(6) atoms/kg) but measurable for the first time in the 100K-Area wells using mass spectrometric analyses that are much more sensitive than alpha spectroscopy methods used previously. Size fractionation data from two wells suggest that 7-29% of the Pu is associated with colloids, operationally defined here as particles between 1 kDa-0.2 microm in size. These colloids were collected using a 1 kDa cross-flow ultrafiltration (CFF) system developed specifically for groundwater actinide studies to include careful controls both in the field and during processing to ensure in situ geochemical conditions are maintained and size separations can be well characterized. Pu in this colloidal fraction was exclusively in the more reduced Pu(III/IV) form, consistent with the higher affinity of Pu in the lower oxidation states for particle surfaces. While the overall concentrations of Pu were low, the Pu isotopic composition suggests at least two local sources of groundwater Pu, namely, local Hanford reactor operations at the 100K-Area and spent nuclear fuel from the N-reactor, which was stored in concrete pools at this site. Differences between this site and the Savannah River Site (SRS) are noted, since groundwater Pu at the F-Area seepage basin at SRS has been found using these same methods, to be characterized by lower colloidal abundances and higher oxidation states. This difference is not directly attributable to groundwater redox potential or geochemical conditions, but rather the physical-chemical difference in Pu sources, which at SRS appear to be dominated downstream from the seepage basins by decay of 244Cm, resulting in more oxidized forms of 240Pu. There is no clear evidence for colloid facilitated transport of Pu in groundwater at the Hanford Site, since downstream wells have both an order of magnitude lower concentrations of Pu and a lower fractional colloidal distribution.     

Rapid transport from the surface to wells in fractured rock: a unique infiltration tracer experiment

A unique infiltration tracer experiment was performed whereby a fluorescent dye was applied to the land surface in an agricultural field, near Perth, Ontario, Canada, to simulate the transport of solutes to two pumped monitoring wells drilled into the granitic gneiss aquifer. This experiment, interpreted using the discrete-fracture capability of the numerical model HydroGeoSphere, showed that solute transport from the surface through thin soil (less than 2m) to wells in fractured bedrock can be extremely rapid (on the order of hours). Also, it was demonstrated that maximum concentrations of contaminants originating from the ground surface will not necessarily be the highest in the shallow aquifer horizon. These are important considerations for both private and government-owned drinking water systems that draw water from shallow fractured bedrock aquifers. This research illustrates the extreme importance of protecting drinking water at the source.     

Combined application of conservative transport modelling and compound-specific carbon isotope analyses to assess in situ attenuation of benzene, toluene, and o-xylene

In recent years, compound specific isotope analyses (CSIA) have developed into one of the most powerful tools for the quantification of in situ biodegradation of organic contaminants. In this approach, the calculation of the extent of biodegradation of organic contaminants in aquifers is usually based on the Rayleigh equation, and thus neglects physical transport processes such as dispersion that contribute to contaminant dilution in aquifers. Here we combine compound specific isotope analyses with a conservative transport model to study the attenuation of aromatic hydrocarbons at a former gasworks site. The conservative transport model was first used to simulate concentration reductions caused by dilution at wells downgradient of a BTEX source. In a second step, the diluted concentrations, together with the available stable carbon isotope ratios and carbon fractionation factors for benzene, toluene and o-xylene were applied in the Rayleigh equation to quantify the degree of biodegradation at each of those wells. At the investigated site, where other attenuation processes such as sorption and volatilisation were proven to be negligible, the combined approach is recommended for benzene, which represents a compound for which the effect of biodegradation is comparable to or less than the effect of dilution. As demonstrated for toluene and o-xylene, the application of the Rayleigh equation alone is sufficient if dilution can be proved to be insignificant in comparison to biodegradation. The analysis also suggests that the source width and the position of the observation wells relative to the plume center line are significantly related to the degree of dilution.     

Variably saturated flow and multicomponent biogeochemical reactive transport modeling of a uranium bioremediation field experiment

Three-dimensional, coupled variably saturated flow and biogeochemical reactive transport modeling of a 2008 in situ uranium bioremediation field experiment is used to better understand the interplay of transport and biogeochemical reactions controlling uranium behavior under pulsed acetate amendment, seasonal water table variation, spatially variable physical (hydraulic conductivity, porosity) and geochemical (reactive surface area) material properties. While the simulation of the 2008 Big Rusty acetate biostimulation field experiment in Rifle, Colorado was generally consistent with behaviors identified in previous field experiments at the Rifle IFRC site, the additional process and property detail provided several new insights. A principal conclusion from this work is that uranium bioreduction is most effective when acetate, in excess of the sulfate-reducing bacteria demand, is available to the metal-reducing bacteria. The inclusion of an initially small population of slow growing sulfate-reducing bacteria identified in proteomic analyses led to an additional source of Fe(II) from the dissolution of Fe(III) minerals promoted by biogenic sulfide. The falling water table during the experiment significantly reduced the saturated thickness of the aquifer and resulted in reactants and products, as well as unmitigated uranium, in the newly unsaturated vadose zone. High permeability sandy gravel structures resulted in locally high flow rates in the vicinity of injection wells that increased acetate dilution. In downgradient locations, these structures created preferential flow paths for acetate delivery that enhanced local zones of TEAP reactivity and subsidiary reactions. Conversely, smaller transport rates associated with the lower permeability lithofacies (e.g., fine) and vadose zone were shown to limit acetate access and reaction. Once accessed by acetate, however, these same zones limited subsequent acetate dilution and provided longer residence times that resulted in higher concentrations of TEAP reaction products when terminal electron donors and acceptors were not limiting. Finally, facies-based porosity and reactive surface area variations were shown to affect aqueous uranium concentration distributions with localized effects of the fine lithofacies having the largest impact on U(VI) surface complexation. The ability to model the comprehensive biogeochemical reaction network, and spatially and temporally variable processes, properties, and conditions controlling uranium behavior during engineered bioremediation in the naturally complex Rifle IFRC subsurface system required a subsurface simulator that could use the large memory and computational performance of a massively parallel computer. In this case, the eSTOMP simulator, operating on 128 processor cores for 12h, was used to simulate the 110-day field experiment and 50 days of post-biostimulation behavior.     

Electrokinetic ion transport through unsaturated soil: 2. Application to a heterogeneous field site

Results of a field demonstration of electrokinetic transport of acetate through an unsaturated heterogeneous soil are compared to numerical modeling predictions. The numerical model was based on the groundwater flow and transport codes MODFLOW and MT3D modified to account for electrically induced ion transport. The 6-month field demonstration was conducted in an unsaturated layered soil profile where the soil moisture content ranged from 4% to 28% (m3 m(-3)). Specially designed ceramic-cased electrodes maintained a steady-state moisture content and electric potential field between the electrodes during the field demonstration. Acetate, a byproduct of acetic acid neutralization of the cathode electrolysis reaction, was transported from the cathode to the anode by electromigration. Field demonstration results indicated preferential transport of acetate through soil layers exhibiting higher moisture content/electrical conductivity. These field transport results agree with theoretical predictions that electromigration velocity is proportional to a power function of the effective moisture content. A numerical model using a homogeneous moisture content/electrical conductivity domain did not adequately predict the acetate field results. Numerical model predictions using a three-layer electrical conductivity/moisture content profile agreed qualitatively with the observed acetate distribution. These results suggest that field heterogeneities must be incorporated into electrokinetic models to predict ion transport at the field-scale.     

The Bechtel Confined Zone dispersion Process for FGD Retrofit Situations Proof-of-Concept Tests

The Bechtel Confined Zone Dispersion (CZD) process for FGD retrofit situations was tested at two sites: one at a level of 5 MWe; the other at 70 MWe. The CZD process involves injecting a finely atomized slurry of hydrated lime into a straight run of duct between a boiler's air heater and its electrostatic precipitator (ESP). The effect of process variables on SO₂ removal and ESP performance was investigated for dolomitic/calcitic lime. Removals of SO₂ in excess of 50 percent were achieved for either lime type at the 5 MWe site. A very short duct length limited injection rate at the 70 MWe site, limiting sulfur removals to a maximum of 30 percent. SO₂ removal data for both sites were successfully correlated on a common basis. ESP performance was not fully acceptable during lime injection at both sites, but it is felt that optimization of ESP operations should eliminate this problem. Additional testing is recommended to further explore ESP performance and to optimize lime injection parameters. The results obtained to date continue to indicate that the CZD process is an attractive and economical candidate for FGD retrofit situations.