Estimating Reaction Rate Coefficients Within a Travel‐Time Modeling Framework

A generalized, efficient, and practical approach based on the travel‐time modeling framework is developed to estimate in situ reaction rate coefficients for groundwater remediation in heterogeneous aquifers. The required information for this approach can be obtained by conducting tracer tests with injection of a mixture of conservative and reactive tracers and measurements of both breakthrough curves (BTCs). The conservative BTC is used to infer the travel‐time distribution from the injection point to the observation point. For advection‐dominant reactive transport with well‐mixed reactive species and a constant travel‐time distribution, the reactive BTC is obtained by integrating the solutions to advective‐reactive transport over the entire travel‐time distribution, and then is used in optimization to determine the in situ reaction rate coefficients. By directly working on the conservative and reactive BTCs, this approach avoids costly aquifer characterization and improves the estimation for transport in heterogeneous aquifers which may not be sufficiently described by traditional mechanistic transport models with constant transport parameters. Simplified schemes are proposed for reactive transport with zero‐, first‐, nth‐order, and Michaelis‐Menten reactions. The proposed approach is validated by a reactive transport case in a two‐dimensional synthetic heterogeneous aquifer and a field‐scale bioremediation experiment conducted at Oak Ridge, Tennessee. The field application indicates that ethanol degradation for U(VI)‐bioremediation is better approximated by zero‐order reaction kinetics than first‐order reaction kinetics.     

Stochastic Cost Optimization of Multistrategy DNAPL Site Remediation

This paper investigates numerical optimization of dense nonaqueous phase liquid (DNAPL) site remediation design considering effects of prediction and measurement uncertainty. Results are presented for a hypothetical problem involving remediation using thermal source reduction (TSR) and bioremediation with electron donor (ED) injection. Pump-and-treat is utilized as a backup measure if compliance criteria are not met. Remediation system design variables are optimized to minimize expected net present value (ENPV) cost. Adaptive criteria are assumed for real-time control of TSR and ED duration. Source zone dissolved concentration data enabled more reliable and lower cost operation of TSR than soil concentration data, but using both soil and dissolved data improved results sufficiently to more than offset the additional cost. Decisions to terminate remediation and monitoring or to initiate pump-and-treat are complicated by measurement noise. Simultaneous optimization of monitoring frequency, averaging period, and lookback periods to confirm decisions, in addition to remediation design variables, reduced ENPV cost. Results indicate that remediation design under conditions of uncertainty is affected by subtle interactions and tradeoffs between design variables, compliance rules, site characteristics, and uncertainty in model predictions and monitoring data. Optimized designs yielded cost savings of up to approximately 50% compared with a nonoptimized design based on common engineering practices. Significant improvements in accuracy and reductions in cost were achieved by recalibrating the model to data collected during remediation and re-optimizing design variables. Repeating this process periodically is advisable to minimize total costs and maximize reliability.     

The Application of In Situ Air Sparging as an Innovative Soils and Ground Water Remediation Technology

Vapor extraction (soil venting) has been demonstrated to be a successful and cost-effective remediation technology for removing VOCs from the vadose (unsaturated) zone. However, in many cases, seasonal water table fluctuations, drawdown associated with pump-and-treat remediation techniques, and spills involving dense, non-aqueous phase liquids (DNAPLS) create contaminated soil below the water table. Vapor extraction alone is not considered to be an optimal remediation technology to address this type of contamination.
An innovative approach to saturated zone remediation is the use of sparging (injection) wells to inject a hydrocarbon-free gaseous medium (typically air) into the saturated zone below the areas of contamination. The contaminants dissolved in the ground water and sorbed onto soil particles partition into the advective air phase, effectively simulating an in situ air-stripping system. The stripped contaminants are transported in the gas phase to the vadose zone, within the radius of influence of a vapor extraction and vapor treatment system.
In situ air sparging is a complex multifluid phase process, which has been applied successfully in Europe since the mid-1980s. To date, site-specific pilot tests have been used to design air-sparging systems. Research is currently underway to develop better engineering design methodologies for the process. Major design parameters to be considered include contaminant type, gas injection pressures and flow rates, site geology, bubble size, injection interval (areal and vertical) and the equipment specifications. Correct design and operation of this technology has been demonstrated to achieve ground water cleanup of VOC contamination to low part-per-billion levels.     

Bioremediation in Fractured Rock: 1. Modeling to Inform Design,Monitoring, and Expectations

Field characterization of a trichloroethene (TCE) source area in fractured mudstones produced a detailed understanding of the geology, contaminant distribution in fractures and the rock matrix, and hydraulic and transport properties. Groundwater flow and chemical transport modeling that synthesized the field characterization information proved critical for designing bioremediation of the source area. The planned bioremediation involved injecting emulsified vegetable oil and bacteria to enhance the naturally occurring biodegradation of TCE. The flow and transport modeling showed that injection will spread amendments widely over a zone of lower‐permeability fractures, with long residence times expected because of small velocities after injection and sorption of emulsified vegetable oil onto solids. Amendments transported out of this zone will be diluted by groundwater flux from other areas, limiting bioremediation effectiveness downgradient. At nearby pumping wells, further dilution is expected to make bioremediation effects undetectable in the pumped water. The results emphasize that in fracture‐dominated flow regimes, the extent of injected amendments cannot be conceptualized using simple homogeneous models of groundwater flow commonly adopted to design injections in unconsolidated porous media (e.g., radial diverging or dipole flow regimes). Instead, it is important to synthesize site characterization information using a groundwater flow model that includes discrete features representing high‐ and low‐permeability fractures. This type of model accounts for the highly heterogeneous hydraulic conductivity and groundwater fluxes in fractured‐rock aquifers, and facilitates designing injection strategies that target specific volumes of the aquifer and maximize the distribution of amendments over these volumes.     

Assessing TCE Source Bioremediation by Geostatistical Analysis of a Flux Fence

Mass discharge across transect planes is increasingly used as a metric for performance assessment of in situ groundwater remediation systems. Mass discharge estimates using concentrations measured in multilevel transects are often made by assuming a uniform flow field, and uncertainty contributions from spatial concentration and flow field variability are often overlooked. We extend our recently developed geostatistical approach to estimate mass discharge using transect data of concentration and hydraulic conductivity, so accounting for the spatial variability of both datasets. The magnitude and uncertainty of mass discharge were quantified by conditional simulation. An important benefit of the approach is that uncertainty is quantified as an integral part of the mass discharge estimate. We use this approach for performance assessment of a bioremediation experiment of a trichloroethene (TCE) source zone. Analyses of dissolved parent and daughter compounds demonstrated that the engineered bioremediation has elevated the degradation rate of TCE, resulting in a two‐thirds reduction in the TCE mass discharge from the source zone. The biologically enhanced dissolution of TCE was not significant (～5%), and was less than expected. However, the discharges of the daughter products cis‐1,2, dichloroethene (cDCE) and vinyl chloride (VC) increased, probably because of the rapid transformation of TCE from the source zone to the measurement transect. This suggests that enhancing the biodegradation of cDCE and VC will be crucial to successful engineered bioremediation of TCE source zones.     

In Situ Destruction of Perchlorate and Nitrate Using Gaseous Electron Donor Injection Technology

Perchlorate and nitrate in vadose‐zone soil can be continuing sources of groundwater contamination and technologies for remediation of these sources are limited. Gaseous electron donor injection technology (GEDIT) is an in situ approach that was demonstrated at a site in California. A mixture of hydrogen, carbon dioxide, liquefied petroleum gas (LPG), and nitrogen was injected into the vadose zone over a period of 5 months followed by 3 months of LPG alone. Perchlorate and nitrate plus nitrite nitrogen concentrations were reduced by over 90% and both were capable of being reduced to nondetectable concentrations. Hydrogen was required for perchlorate destruction, although concentrations as low as 0.5% were effective. Hydrogen was not required for nitrate destruction. Contaminant destruction was observed in both fine‐grained and coarse‐grained soils ranging from clay to gravel. Hydrogen was an effective electron donor because of its low molecular weight and high diffusivity which likely promoted its penetration into low‐permeability formations. Contaminant destruction was also observed in moisture contents ranging from 6.8% to 36% demonstrating that GEDIT was effective in low‐ and high‐moisture soils. The radius of influence (ROI) for perchlorate destruction was approximately 3.0 to 4.6 m while that for nitrate was greater than 17 m. The ROI was limited by use of a single injection location. Use of a grid injection system is anticipated to greatly increase efficiency. This research represents the first demonstration of GEDIT for treatment of contaminants in the vadose zone.     

Evaluation of Combined Direct-Push Methods Used for Aquifer Model Generation

Most established methods to characterize aquifer structure and hydraulic conductivities of hydrostratigraphical units are not capable of delivering sufficient information in the spatial resolution that is desired for sophisticated numerical contaminant transport modeling and adapted remediation design. With hydraulic investigation methods based on the direct-push (DP) technology such as DP slug tests, DP injection logging, and the hydraulic profiling tool, it is possible to rapidly delineate hydrogeological structures and estimate their hydraulic conductivity in shallow unconsolidated aquifers without the need for wells. A combined application of these tools was used for the investigation of a contaminated German refinery site and for the setup of hydraulic aquifer models. The quality of DP investigation and the models was evaluated by comparisons of tracer transport simulations using these models and measured breakthroughs of two natural gradient tracer tests. Model scenarios considering the information of all tools together showed good reproduction of the measured breakthroughs, indicating the suitability of the approach and a minor impact of potential technical limitations. Using the DP slug tests alone yielded significantly higher deviations for the determined hydraulic conductivities compared to considering two or three of the tools. Realistic aquifer models developed on basis of such combined DP investigation approaches can help optimize remediation concepts or identify flow regimes for aquifers with a complex structure.     

Ground Water Sampling Bias Observed in Shallow, Conventional Wells

A previous field demonstration project on nitrate-based bioremediation of a fuel-contaminated aquifer used short-screened clustered well points in addition to shallow (10 foot), conventional monitoring wells to monitor the progress of remediation during surface application of recharge. These well systems were placed in the center and at one edge of each of two treatment cells. One cell received recharge amended with nitrate (nitrate cell), and the other received unamended recharge (control cell). Data from the clustered well points were averaged to provide a mean estimate for comparison with the associated conventional monitoring well.
Conservative tracer profiles were similar for each of the four systems, with better fits obtained for well systems located at the edge of the treatment cells. However, aromatic hydrocarbon and electron acceptor profiles varied greatly for the two center well systems, with the conventional monitoring well data suggesting that remediation was proceeding at a much more rapid rate than indicated by the cluster well points. Later tests with an electromagnetic borehole flowmeter demonstrated a significant vertical flow through the well-bore of the conventional monitoring well under simulated operating conditions. This created an artifact during sampling, thought to arise from preferential flow of recharge water from the water table to deeper portions of the contaminated zone resulting in several effects, including an actual decreased residence time of water sampled by the conventional well. These data provide additional evidence that conventional monitoring wells may be inadequate for monitoring remediation in the presence of significant vertical hydraulic gradients, even for fairly shallow homogeneous aquifers.     

Demonstration of Enhanced Bioremediation in a TCE Source Area at Launch Complex 34, Cape Canaveral Air Force Station

The ability of bioremediation to treat a source area containing trichloroethene (TCE) present as dense nonaqueous phase liquid (DNAPL) was assessed through a laboratory study and a pilot test at Launch Complex 34, Cape Canaveral Air Force Center. The results of microcosm testing indicate that the indigenous microbial community was capable of dechlorinating TCE to ethene if amended with electron donor; however, bioaugmentation with a dechlorinating culture (KB-1; SiREM, Guelph, Ontario, Canada) significantly increased the rate of ethene formation. In microcosms, the activity of the dechlorinating organisms in KB-1 was not inhibited at initial TCE concentrations as high as 2 mM. The initially high TCE concentration in ground water (1.2 mM or 155 mg/L) did not inhibit reductive dechlorination, and at the end of the study, the average concentration of ethene (2.4 mM or 67 mg/L) was in stoichiometric excess of this initial TCE concentration. The production of ethene in stoichiometric excess in comparison to the initial TCE concentration indicates that the bioremediation treatment enhanced the removal of TCE mass (either sorbed to soil or present as DNAPL). Detailed soil sampling indicated that the bioremediation treatment removed greater than 98.5% of the initial TCE mass. Confirmatory ground water samples collected 22 months after the bioremediation treatment indicated that chloroethene concentrations had continued to decline in the absence of further electron donor addition. The results of this study confirm that dechlorination to ethene can proceed at the high TCE concentrations often encountered in source areas and that bioremediation was capable of removing significant TCE mass from the test plot, suggesting that enhanced bioremediation is a potentially viable remediation technology for TCE source areas. Dehalococcoides abundance increased by 2 orders of magnitude following biostimulation and bioaugmentation.     

Cost Optimization of DNAPL Remediation at Dover Air Force Base Site

This study investigates stochastic optimization of dense nonaqueous phase liquid (DNAPL) remediation design at Dover Air Force Base Area 5 using emulsified vegetable oil (EVO) injection. The Stochastic Cost Optimization Toolkit (SCOToolkit) is used for the study, which couples semianalytical DNAPL source depletion and transport models with parameter estimation, error propagation, and stochastic optimization modules that can consider multiple sources and remediation strategies. Model parameters are calibrated to field data conditions on prior estimates of parameters and their uncertainty. Monte Carlo simulations are then performed to identify optimal remediation decisions that minimize the expected net present value (NPV) cleanup cost while maintaining concentrations at compliance wells under the maximum contaminant level (MCL). The results show that annual operating costs could be reduced by approximately 50% by implementing the identified optimal remediation strategy. We also show that recalibration and reoptimization after 50 years using additional monitoring data could lead to a further 60% reduction in annual operating cost increases the reliability of the proposed remediation actions.     

Modeling and Remediation of Ground Water Contamination at the Engelse Werk Wellfield

Contaminants have been threatening the Engelse Werk wellfield located between the town of Zwolle and the IJssel River in the Netherlands. Chemical analysis of water samples taken in production wells, both at the IJssel River and near the Zwolle railway station, indicated elevated concentrations of mainly organic contaminants including benzene, bentazon, acenaftene, trichloroethane, and bromacil. Immediate contaminant prevention and remediation measures are needed to safeguard the production wells. Ground water flow and transport models were developed to assist in the design of remediation strategies. Ground water flow models indicated that the IJssel River and a waste disposal ditch at the railway station are within the capture zone of the wellfield. A chloride transport model simulated minimum travel times in the order of four to 13 years for contaminants in the IJssel River to reach the production wells of the wellfield. A transport model for benzene was set up to advise on the remediation measures to be taken at the waste disposal ditch to clean up the contamination in the upper aquifer between this site and the Engelse Werk wellfield. The designed remediation system consists of 12 pumping wells with a combined capacity of 1650 m³/day. The system is capable of reducing the benzene levels at the threatened production wells at the Engelse Werk wellfield to a permissible level below 0.1 μg/L within a period of 5 years.     

A program for evaluating dual-equilibrium desorption effects on remediation

Desorption is one of the most critical processes affecting the effectiveness of soil and ground water remediation. None of the currently adopted desorption models can accurately quantify desorption of low-hydrophobicity organic chemicals, and thus could potentially mislead remediation design and decision-making. A recently developed dual-equilibrium desorption (DED) model was found to be much more accurate in quantifying desorption. A screening-level transport model, DED-Transport, was developed to simulate the DED effect on behaviors of organic contaminant plumes during remediation. DED-Transport requires only simple parameters, but is applicable to many remediation scenarios. DED-Transport can be used as a decision-support tool in site remediation to more precisely predict the time required for cleanup.     

Modeling a Ground Water Circulation Well Alternative

Ground water circulation wells (GCWs) provide an appealing alternative to typical pump-and-treat ground water remediation systems because of the inherent resource-conservative nature of the GCW systems. GCW performance prediction is challenging because the consideration of extraction and recharge in a single well is unusual for most practitioners, the technology is relatively new, and a meaningful body of literature has not been published. A three-part evaluation process using state-of-the-practice numerical ground water flow and mass transport models was developed for application during GCW pilot studies at the former Nebraska Ordnance Plant site. A small-scale ground water flow model was developed during the pilot study planning process to predict the system performance and to locate performance-measuring monitoring wells. Key predictions included the capture zone predicted to develop upgradient of the GCW, the downgradierit GCW recharge zone, and the circulation zone centered on the GCW. The flow model was subsequently verified using ground water elevation data and contaminant concentration data collected during pilot study operation. Aquifer parameters were reestimated as a result of the verification process. Those parameter values were used as input to a larger scale model, which was used to develop a remedial alternative consisting of multiple GCW systems.     

Estimating Persistent Mass Flux of Volatile Contaminants from the Vadose Zone to Ground Water

Contaminants may persist for long time periods within low permeability portions of the vadose zone where they cannot be effectively treated and are a potential continuing source of contamination to ground water. Setting appropriate vadose zone remediation goals typically requires evaluating these persistent sources in terms of their impact on meeting ground water remediation goals. Estimating the impact on ground water can be challenging at sites with low aqueous recharge rates where vapor-phase movement is the dominant transport process in the vadose zone. Existing one-dimensional approaches for simulating transport of volatile contaminants in the vadose zone are considered and compared to a new flux-continuity-based assessment of vapor-phase contaminant movement from the vadose zone to the ground water. The flux-continuity-based assessment demonstrates that the ability of the ground water to move contaminant away from the water table controls the vapor-phase mass flux from the vadose zone across the water table. Limitations of these approaches are then discussed with respect to the required assumptions and the need to incorporate three-dimensional processes when evaluating vapor-phase transport from the vadose zone to the ground water. The carbon tetrachloride plume at the U.S. Department of Energy Hanford Site is used as the example site where persistent vadose zone contamination needs to be considered in the context of ground water remediation.     

Remediation of Heterogeneous Aquifers Subject to Uncertainty

Optimal cost pump-and-treat ground water remediation designs for containment of a contaminated aquifer are often developed using deterministic ground water models to predict ground water flow. Uncertainty in hydraulic conductivity fields used in these models results in remediation designs that are unreliable. The degree to which uncertainty contributes to the reliability of remediation designs as measured by the characterization of the uncertainty is shown to differ depending upon the geologic environments of the models. This conclusion is drawn from the optimal design costs for multiple deterministic models generated to represent the uncertainty of four distinct models with different geologic environments. A multi scenario approach that includes uncertainty into the remediation design called the deterministic method for optimization subject to uncertainty (DMOU) is applied to these distinct models. It is found that the DMOU is a method for determining a remediation design subject to uncertainty that requires minimal postprocessing efforts. Preprocessing, however, is required for the application of the DMOU to unique problems. In the ground water remediation design problems, the orientation of geologic facies with respect to the orientation of flow patterns, pumping well locations, and constraint locations are shown to affect the preprocessing, the solutions to the DMOU problems, and the computational efficiency of the DMOU approach. The results of the DMOU are compared to the results of a statistical analysis of the effects of the uncertainty on remediation designs. This comparison validates the efficacy of the DMOU and illustrates the computational advantages to using the DMOU over statistical measures.     

An Investigation of the Pressure Pulsing Reagent Delivery Approach

Pressure pulsing technology is an innovative method that has been developed with the aim of overcoming preferred flow paths associated with remediation techniques that rely on the injection of reagents. Numerical and field experiments were conducted to assess how pressure pulsing affects groundwater flow and solute transport during reagent injection. A series of field experiments were performed at two field sites where a monitoring network designed to capture the breakthrough of solutes delivered from an injection well was installed. Pressure pulsing and conventional injection methods were used at each site. One site was comprised of fine sand with low heterogeneity, while the other was moderately heterogeneous with discrete layers varying from fine sand to silt. The data suggest that breakthrough was more uniform for the pressure pulsing injections; however, this difference was minor and complicated by sorption of some of the tracers employed. The groundwater flow and solute transport modeling exercise simulated the rapid boundary pressure modulation that occurs in association with pressure pulsing. Two‐dimensional (2D) simulations revealed that repeated sudden onset of injection cessation produces brief periods of gradient reversal and the development of a mixing zone near the injection well. The spatial extents of this mixing zone were found to be highly dependent upon the hydraulic diffusivity of the medium, with medium heterogeneity and pulsing frequency playing secondary roles. Three‐dimensional (3D) numerical simulations were used to benchmark the observations from one of the field sites. The results from the modeling effort showed that solute breakthrough from a pressure pulsing injection is more dispersed relative to a conventional injection as a result of the mixing zone phenomenon; however, we were unable to directly observe this mixing zone using the instrumentation deployed at the two field sites.     

Removal of Volatile Organic Compounds in Vertical Flow Filters: Predictions from Reactive Transport Modeling

Vertical flow filters are containers filled with porous medium that are recharged from top and drained at the bottom, and are operated at partly saturated conditions. They have recently been suggested as treatment technology for groundwater containing volatile organic compounds (VOCs). Numerical reactive transport simulations were performed to investigate the relevance of different filter operation modes on biodegradation and/or volatilization of the contaminants and to evaluate the potential limitation of such remediation mean due to volatile emissions. On the basis of the data from a pilot‐scale vertical flow filter intermittently fed with domestic waste water, model predictions on the system’s performance for the treatment of contaminated groundwater were derived. These simulations considered the transport and aerobic degradation of ammonium and two VOCs, benzene and methyl tertiary butyl ether (MTBE). In addition, the advective‐diffusive gas‐phase transport of volatile compounds as well as oxygen was simulated. Model predictions addressed the influence of depth and frequency of the intermittent groundwater injection, degradation rate kinetics, and the composition of the filter material. Simulation results show that for unfavorable operation conditions significant VOC emissions have to be considered and that operation modes limiting VOC emissions may limit aerobic biodegradation. However, a suitable combination of injection depth and composition of the filter material does facilitate high biodegradation rates while only little VOC emissions take place. Using such optimized operation modes would allow using vertical flow filter systems as remediation technology suitable for groundwater contaminated with volatile compounds.     

Bioavailability of Hydrophobic Organic Contaminants: Effects and Implications of Sorption-Related Mass Transfer on Bioremediation

The low bioavailability of hydrophobic organic compounds (HOCs) is one of the key sources of uncertainty in the implementation of in situ bioremediation. Bioavailability of HOCs in the subsurface is affected by sorption/desorption processes in two important ways. First, sorption causes high organic concentrations in microporous regions and impermeable zones to which bacterial access is obstructed. Second, because desorption and immobile zone diffusion must occur before biodegradation can proceed, the overall rate of bioremediation can be limited or even controlled by these mass transfer processes, not by the activity of the degrading microorganisms. Rate models that couple sorption/desorption—related mass transfer processes and biodegradation have been successfully applied to laboratory results and are beginning to offer some insight into the problem. Specifically, the influence of sorption on biodegradation is quantified here by defining a bioavailability factor, B_f. However, many questions remain and predictive modeling is elusive, especially in the context of complicated heterogeneous natural systems. Challenges facing environmental engineers are to develop a better understanding of these processes at both laboratory and field scales and ultimately to use such understanding toward the development of more effective and economical remediation technologies.