Groundwater remediation: the next 30 years

Groundwater remediation technologies are designed, installed, and operated based on the conceptual models of contaminant hydrogeology that are accepted at that time. However, conceptual models of remediation can change as new research, new technologies, and new performance data become available. Over the past few years, results from multiple-site remediation performance studies have shown that achieving drinking water standards (i.e., Maximum Contaminant Levels, MCLs) at contaminated groundwater sites is very difficult. Recent groundwater research has shown that the process of matrix diffusion is one key constraint. New developments, such as mass discharge, orders of magnitude (OoMs), and SMART objectives are now being discussed more frequently by the groundwater remediation community. In this paper, the authors provide their perspectives on the existing "reach MCLs" approach that has historically guided groundwater remediation projects, and advocate a new approach built around the concepts of OoMs and mass discharge.     

A Coupled Groundwater–Surface Water Modeling Framework for Simulating Transition Zone Processes

There is an identified need for fully representing groundwater–surface water transition zone (i.e., the sediment zone that connects groundwater and surface water) processes in modeling fate and transport of contaminants to assist with management of contaminated sediments. Most existing groundwater and surface water fate and transport models are not dynamically linked and do not consider transition zone processes such as bioturbation and deposition and erosion of sediments. An interface module is developed herein to holistically simulate the fate and transport by coupling two commonly used models, Environmental Fluid Dynamics Code (EFDC) and SEAWAT, to simulate surface water and groundwater hydrodynamics, while providing an enhanced representation of the processes in the transition zone. Transition zone and surface water contaminant processes were represented through an enhanced version of the EFDC model, AQFATE. AQFATE also includes SEDZLJ, a state‐of‐the‐science surface water sediment transport model. The modeling framework was tested on a published test problem and applied to evaluate field‐scale two‐ and three‐dimensional contaminant transport. The model accurately simulated concentrations of salinity from a published test case. For the field‐scale applications, the model showed excellent mass balance closure for the transition zone and provided accurate simulations of all transition zone processes represented in the modeling framework. The model predictions for the two‐dimensional field case were consistent with site‐specific observations of contaminant migration. This modeling framework represents advancement in the simulation of transition zone processes and can help inform risk assessment at sites where contaminant sources from upland areas have the potential to impact sediments and surface water.     

Lessons Learned from 25 Years of Research at the MADE Site

Field studies at well‐instrumented research sites have provided extensive data sets and important insights essential for development and testing of transport theories and mathematical models. This paper provides an overview of over 25 years of research and lessons learned at one of such field research sites on the Columbus Air Force Base in Mississippi, commonly known as the Macrodispersion Experiment (MADE) site. Since the mid‐1980s, field data from the MADE site have been used extensively by researchers around the world to explore complex contaminant transport phenomena in highly heterogeneous porous media. Results from field investigations and modeling analyses suggested that connected networks of small‐scale preferential flow paths and relative flow barriers exert dominant control on solute transport processes. The classical advection‐dispersion model was shown to inadequately represent plume‐scale transport, while the dual‐domain mass transfer model was found to reproduce the primary observed plume characteristics. The MADE site has served as a valuable natural observatory for contaminant transport studies where new observations have led to better understanding and improved models have sprung out analysis of new data.     

Composite analytical solutions for a soil vapour extraction system

Soil vapour extraction (SVE) is a common remediation technique for cleaning up unsaturated soils contaminated by volatile organic compounds (VOCs). Analytical solutions, which result from simple mathematical models, can allow the fast approximation of the time‐dependent effluent concentration and the gaining of insight into the processes that take place during soil remediation. Deriving the analytical solutions to advection–dispersion equations that simultaneously take into account the mechanical dispersion and molecular diffusion is very difficult because of the variable dependence of governing equations' coefficients. In this study, we first present two simplified analytical solutions that only consider mechanical dispersion or molecular diffusion. The two developed analytical solutions are compared with the numerical solution that simultaneously considers both mechanical dispersion and molecular diffusion to examine the applicability of the two simplified analytical solutions and distinguishes the individual contribution of the mechanical dispersion and molecular diffusion to total VOCs transport in an SVE system. Results show that dispersion plays an important role during SVE decontamination and neither the diffusion‐dominated solution nor the dispersion‐dominated solution can agree well with the numerical solution when both mechanical dispersion and molecular diffusion have significant contributions to the total VOCs transport flux. A composite analytical solution that linearly couples the diffusion‐ and dispersion‐dominated analytical solutions, which is proposed herein to eliminate the discrepancy between the analytical solutions and the numerical solution. Results indicate that the proposed composite analytical solution agrees well with the numerical solution and is an effective tool for quickly and accurately evaluating the time‐dependent effluent concentration for parameters of the different ranges of interest in an SVE remedial system. Copyright © 2006 John Wiley & Sons, Ltd.     

Understanding the Geometry of Connected Fracture Flow with Multiperiod Oscillatory Hydraulic Tests

An understanding of the spatial and hydraulic properties of fast preferential flow pathways in the subsurface is necessary in applications ranging from contaminant fate and transport modeling to design of energy extraction systems. One method for the characterization of fracture properties over interwellbore scales is Multiperiod Oscillatory Hydraulic (MOH) testing, in which the aquifer response to oscillatory pressure stimulations is observed. MOH tests were conducted on isolated intervals of wells in siliciclastic and carbonate aquifers in southern Wisconsin. The goal was to characterize the spatial properties of discrete fractures over interwellbore scales. MOH tests were conducted on two discrete fractured intervals intersecting two boreholes at one field site, and a nest of three piezometers at another field site. Fracture diffusivity estimates were obtained using analytical solutions that relate diffusivity to observed phase lag and amplitude decay. In addition, MOH tests were used to investigate the spatial extent of flow using different conceptual models of fracture geometry. Results indicated that fracture geometry at both field sites can be approximated by permeable two‐dimensional fracture planes, oriented near‐horizontally at one site, and near‐vertically at the other. The technique used on MOH field data to characterize fracture geometry shows promise in revealing fracture network characteristics important to groundwater flow and transport.     

Lessons learned from a suite of CFB Borden experiments

This article summarizes several of many field-based studies of subsurface contaminant transport conducted over the last 30 years at the Canadian Forces Base (CFB) Borden site. The field research initially consisted of extensive monitoring of a leachate plume from an abandoned landfill and its analytical and numerical modeling. Lessons learned from these initial studies led to the execution and interpretation of a variety of tracer tests involving conservative and reactive/organic solutes tests performed at various scales. The lessons learned from these tracer tests revealed a number of deficiencies in classical theories of contaminant dispersion and reaction processes as they occur in groundwater, and thus spawned a new era of process-oriented research within the hydrogeological community. The extensively monitored tracer tests were followed by controlled spills of organic contaminants to observe their subsurface movement and distribution as well as the emplacement of a variety of contaminant sources in the saturated and unsaturated zones to study the ambient transport of contaminants. The controlled spills and emplaced sources of various contaminants were then utilized for testing various active and passive remediation technologies. These studies have led to fundamental insights and lessons learned that have significantly contributed to research on contaminant transport in both the saturated and unsaturated zones. Over the years, data generated by the University of Waterloo (UW) researchers and their collaborators continues to be examined by various research groups and has led to additional new insights on subsurface transport of various chemicals.     

Optimal Field Approaches for Electrokinetic In Situ Oxidation Remediation

Numerical simulations were used to identify and evaluate optimum electrode configurations and approaches for electrokinetic in situ chemical oxidation (EK‐ISCO) remediation of low‐permeability sediments. A newly developed groundwater and EK flow and reactive transport numerical model was used to conduct two‐dimensional scenario simulations of the coverage of an injected oxidant, permanganate, and the oxidation of a typical organic contaminant (tetrachloroethene, PCE). For linear configurations of vertical electrodes, the spacing of same‐polarity electrodes is recommended to be about one‐third to one‐quarter of the anode–cathode spacing. Greater coverage could also be achieved by locating additional oxidant injection wells at the divergence of the electric field in linear electrode configurations. Horizontal electrodes allowed greater contact between the injected permanganate and PCE and resulted in faster degradation of PCE compared to vertical electrodes. Pulsed oxidant injection, closer electrode spacing, and electric field reversal also resulted in faster EK‐ISCO remediation.     

Examining the Use of USEPA's Generic Attenuation Factor in Determining Groundwater Screening Levels for Vapor Intrusion

A value of 0.001 is recommended by the United States Environmental Protection Agency (USEPA) for its groundwater‐to‐indoor air Generic Attenuation Factor (GAFG), used in assessing potential vapor intrusion (VI) impacts to indoor air, given measured groundwater concentrations of volatile chemicals of concern (e.g., chlorinated solvents). The GAFG can, in turn, be used for developing groundwater screening levels for VI given target indoor air quality screening levels. In this study, we examine the validity and applicability of the GAFG both for predicting indoor air impacts and for determining groundwater screening levels. This is done using both analysis of published data and screening model calculations. Among the 774 total paired groundwater‐indoor air measurements in the USEPA's VI database (which were used by that agency to generate the GAFG) we found that there are 427 pairs for which a single groundwater measurement or interpolated value was applied to multiple buildings. In one case, up to 73 buildings were associated with a single interpolated groundwater value and in another case up to 15 buildings were associated with a single groundwater measurement (i.e., that the indoor air contaminant concentrations in all of the associated buildings were influenced by the concentration determined at a single point). In more than 70% of the cases (390 of 536 paired measurements in which horizontal building‐monitoring well distance was recorded) the monitoring wells were located more than 30 m (and one up to over 200 m) from the associated buildings. In a few cases, the measurements in the database even improbably implied that soil gas contaminant concentrations increased, rather than decreased, in an upward direction from a contaminant source to a foundation slab. Such observations indicate problematic source characterization within the data set used to generate the GAFG, and some indicate the possibility of a significant influence of a preferential contaminant pathway. While the inherent value of the USEPA database itself is not being questioned here, the above facts raise the very real possibility that the recommended groundwater attenuation factors are being influenced by variables or conditions that have not thus far been fully accounted for. In addition, the predicted groundwater attenuation factors often fall far beyond the upper limits of predictions from mathematical models of VI, ranging from screening models to detailed computational fluid dynamic models. All these models are based on the same fundamental conceptual site model, involving a vadose zone vapor transport pathway starting at an underlying uniform groundwater source and leading to the foundation of a building of concern. According to the analysis presented here, we believe that for scenarios for which such a “traditional” VI pathway is appropriate, 10^?4 is a more appropriately conservative generic groundwater to indoor air attenuation factor than is the EPA‐recommended 10^?3. This is based both on the statistical analysis of USEPA's VI database, as well as the traditional mathematical models of VI. This result has been validated by comparison with results from some well‐documented field studies.     

Total variation diminishing schemes for pollutant transport in porous media

A bidimensional numerical model has been used in order to simulate the contaminant transport in the coastal groundwater area (Atlantic margin of the Rharb basin, Morocco). This groundwater is materialized by means of the salt contamination derived from several factors: evapotranspiration, lithological series formations, marine intrusion, and processes of interaction between water and rocks. In order to reduce the numerical diffusion and limit the numerical dispersion, we use the Superbee flux limiter as a total variation diminishing scheme to discretize the convective operator. This kind of discretization was applied to the coastal groundwater of the Rharb basin (Morocco). The results show that the Superbee flux limiter is efficient at drawing the path of the contaminant front with high accuracy. Consequently, this scheme could constitute an approach in water management and allows one to prevent the risks of pollution and to manage the groundwater resource from a durable development perspective. Copyright © 2007 John Wiley & Sons, Ltd.     

Incorporating Super‐Diffusion due to Sub‐Grid Heterogeneity to Capture Non‐Fickian Transport

Numerical transport models based on the advection‐dispersion equation (ADE) are built on the assumption that sub‐grid cell transport is Fickian such that dispersive spreading around the average velocity is symmetric and without significant tailing on the front edge of a solute plume. However, anomalous diffusion in the form of super‐diffusion due to preferential pathways in an aquifer has been observed in field data, challenging the assumption of Fickian dispersion at the local scale. This study develops a fully Lagrangian method to simulate sub‐grid super‐diffusion in a multidimensional regional‐scale transport model by using a recent mathematical model allowing super‐diffusion along the flow direction given by the regional model. Here, the time randomizing procedure known as subordination is applied to flow field output from MODFLOW simulations. Numerical tests check the applicability of the novel method in mapping regional‐scale super‐diffusive transport conditioned on local properties of multidimensional heterogeneous media.     

Field Study of Subsurface Heterogeneity with Steady‐State Hydraulic Tomography

Remediation of subsurface contamination requires an understanding of the contaminant (history, source location, plume extent and concentration, etc.), and, knowledge of the spatial distribution of hydraulic conductivity (K) that governs groundwater flow and solute transport. Many methods exist for characterizing K heterogeneity, but most if not all methods require the collection of a large number of small‐scale data and its interpolation. In this study, we conduct a hydraulic tomography survey at a highly heterogeneous glaciofluvial deposit at the North Campus Research Site (NCRS) located at the University of Waterloo, Waterloo, Ontario, Canada to sequentially interpret four pumping tests using the steady‐state form of the Sequential Successive Linear Estimator (SSLE) ( Yeh and Liu 2000 ). The resulting three‐dimensional (3D) K distribution (or K‐tomogram) is compared against: ( 1 ) K distributions obtained through the inverse modeling of individual pumping tests using SSLE, and ( 2 ) effective hydraulic conductivity (K_eff) estimates obtained by automatically calibrating a groundwater flow model while treating the medium to be homogeneous. Such a K_eff is often used for designing remediation operations, and thus is used as the basis for comparison with the K‐tomogram. Our results clearly show that hydraulic tomography is superior to the inversions of single pumping tests or K_eff estimates. This is particularly significant for contaminated sites where an accurate representation of the flow field is critical for simulating contaminant transport and injection of chemical and biological agents used for active remediation of contaminant source zones and plumes.     

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.     

Estimating the Impact of Vadose Zone Sources on Groundwater to Support Performance Assessment of Soil Vapor Extraction

Soil vapor extraction (SVE) is a prevalent remediation remedy for volatile organic compound (VOC) contaminants in the vadose zone. To support selection of an appropriate condition at which SVE may be terminated for site closure or for transition to another remedy, an evaluation is needed to determine whether vadose zone VOC contamination has been diminished sufficiently to keep groundwater concentrations below threshold values. A conceptual model for this evaluation was developed for VOC fate and transport from a vadose zone source to groundwater when vapor‐phase diffusive transport is the dominant transport process. A numerical analysis showed that, for these conditions, the groundwater concentration is controlled by a limited set of parameters, including site‐specific dimensions, vadose zone properties, and source characteristics. On the basis of these findings, a procedure was then developed for estimating groundwater concentrations using results from the three‐dimensional multiphase transport simulations for a matrix of parameter value combinations and covering a range of potential site conditions. Interpolation and scaling processes are applied to estimate groundwater concentrations at compliance (monitoring) wells for specific site conditions of interest using the data from the simulation results. The interpolation and scaling methodology using these simulation results provides a far less computationally intensive alternative to site‐specific three‐dimensional multiphase site modeling, while still allowing for parameter sensitivity and uncertainty analyses. With iterative application, the approach can be used to consider the effect of a diminishing vadose zone source over time on future groundwater concentrations. This novel approach and related simulation results have been incorporated into a user‐friendly Microsoft® Excel®‐based spreadsheet tool entitled SVEET (Soil Vapor Extraction Endstate Tool), which has been made available to the public.     

Time‐Lapse Electrical Geophysical Monitoring of Amendment‐Based Biostimulation

Biostimulation is increasingly used to accelerate microbial remediation of recalcitrant groundwater contaminants. Effective application of biostimulation requires successful emplacement of amendment in the contaminant target zone. Verification of remediation performance requires postemplacement assessment and contaminant monitoring. Sampling‐based approaches are expensive and provide low‐density spatial and temporal information. Time‐lapse electrical resistivity tomography (ERT) is an effective geophysical method for determining temporal changes in subsurface electrical conductivity. Because remedial amendments and biostimulation‐related biogeochemical processes often change subsurface electrical conductivity, ERT can complement and enhance sampling‐based approaches for assessing emplacement and monitoring biostimulation‐based remediation. Field studies demonstrating the ability of time‐lapse ERT to monitor amendment emplacement and behavior were performed during a biostimulation remediation effort conducted at the Department of Defense Reutilization and Marketing Office (DRMO) Yard, in Brandywine, Maryland, United States. Geochemical fluid sampling was used to calibrate a petrophysical relation in order to predict groundwater indicators of amendment distribution. The petrophysical relations were field validated by comparing predictions to sequestered fluid sample results, thus demonstrating the potential of electrical geophysics for quantitative assessment of amendment‐related geochemical properties. Crosshole radar zero‐offset profile and borehole geophysical logging were also performed to augment the data set and validate interpretation. In addition to delineating amendment transport in the first 10 months after emplacement, the time‐lapse ERT results show later changes in bulk electrical properties interpreted as mineral precipitation. Results support the use of more cost‐effective surface‐based ERT in conjunction with limited field sampling to improve spatial and temporal monitoring of amendment emplacement and remediation performance.     

The impact of well‐field configuration on contaminant mass removal and plume persistence for homogeneous versus layered systems

A three‐dimensional numerical model was used to simulate the impact of different well‐field configurations on pump‐and‐treat mass removal efficiency for large groundwater contaminant plumes residing in homogeneous and layered domains. Four well‐field configurations were tested, Longitudinal, Distributed, Downgradient, and natural gradient (with no extraction wells). The reductions in contaminant mass discharge (CMDR) as a function of mass removal (MR) were characterized to assess remediation efficiency. Systems whose CDMR‐MR profiles are below the 1:1 relationship curve are associated with more efficient well‐field configurations. For simulations conducted with the homogeneous domain, the CMDR‐MR curves shift leftward, from convex‐downward profiles for natural gradient and Longitudinal to first‐order behaviour for Distributed, and further leftward to a sigmoidal profile for the Downgradient well‐field configuration. These results reveal the maximum potential impacts of well‐field configuration on mass‐removal behaviour, which is attributed to mass‐transfer constraints associated with regions of low flow. In contrast, for the simulations conducted with the layered domain, the CMDR‐MR relationships for the different well‐field configurations exhibit convex‐upward profiles. The nonideal mass‐removal behaviour in this case is influenced by both well‐field configuration and back diffusion associated with low‐permeability units.     

A Practical Modeling Framework for Non‐Fickian Transport and Multi‐Species Sequential First‐Order Reaction

Many studies indicate that small‐scale heterogeneity and/or mobile–immobile mass exchange produce transient non‐Fickian plume behavior that is not well captured by the use of the standard, deterministic advection‐dispersion equation (ADE). An extended ADE modeling framework is presented here that is based on continuous time random walk theory. It can be used to characterize non‐Fickian transport coupled with simultaneous sequential first‐order reactions (e.g., biodegradation or radioactive decay) for multiple degrading contaminants such as chlorinated solvents, royal demolition explosive, pesticides, and radionuclides. To demonstrate this modeling framework, new transient analytical solutions are derived and are inverted in Laplace space. Closed‐form, steady‐state, multi‐species analytical solutions are also derived for non‐Fickian transport in highly heterogeneous aquifers with linear sorption–desorption and matrix diffusion for use in spreadsheets. The solutions are general enough to allow different degradation rates for the mobile and immobile zones. The transient solutions for multi‐species transport are applied to examine the effects of source remediation on the natural attenuation of downgradient plumes of both parent and degradation products in highly heterogeneous aquifers. Results for representative settings show that the use of the standard, deterministic ADE can over‐estimate cleanup rates and under‐predict the cleanup timeframe in comparison to the extended ADE analytical model. The modeling framework and calculations introduced here are also applied for a 30 year groundwater cleanup program at a site in Palm Bay, Florida. The simulated plume concentrations using the extended ADE exhibited agreement with observed long concentration tails of trichloroethene, cis 1,2 DCE, and VC that remained above cleanup goals.     

Issues and Options in the Delineation of Well Capture Zones under Uncertainty

The delineation of wellhead protection areas (WHPAs) under uncertainty is still a challenge for heterogeneous porous media. For granular media, one option is to combine particle tracking (PT) with the Monte Carlo approach (PT‐MC) to account for geologic uncertainties. Fractured porous media, however, require certain restrictive assumptions under this approach. An alternative for all types of media is the capture probability (CP) approach, which is based on the solution of the standard advection‐dispersion equation in a backward mode, making use of the analogy between forward and backward transport processes. Within this context, we review the current controversy about the correct form of the conceptual model for transport, finding that the advection‐diffusion model, which represents the diffusive interchange between streamtubes with differing velocities, is more physically realistic than the conventional advection‐dispersion model. For mildly to moderately heterogeneous materials, stochastic theories and simulation experiments show that this process converges at the field scale to an effective advection‐dispersion process that can be simulated with conventional transport models using appropriate macrodispersivity values. For highly heterogeneous materials, stochastic theories do not yet exist but there is no reason why the process should not converge naturally as well. Macrodispersivities appear to be formation‐specific. The advection‐dispersion model can be used for capture zone delineation in heterogeneous granular media. For fractured porous systems, hybrid equivalent porous medium and discrete fracture network or CP‐based approaches may have potential. In general, capture zones delineated by PT without MC will always be too small and should not be used as a basis for land‐use decisions.     

Uncertainty propagation of hydrodispersive transfer in an aquifer: an illustration of one-dimensional contaminant transport with slug injection

It is evident that the hydrodynamic dispersion coefficient and linear flow velocity dominate solute transport in aquifers. Both of them play important roles characterizing contaminant transport. However, by definition, the parameter of contaminant transport cannot be measured directly. For most problems of contaminant transport, a conceptual model for solute transport generally is established to fit the breakthrough curve obtained from field testing, and then suitable curve matching or the inverse solution of a theoretical model is used to determine the parameter. This study presents a one-dimensional solute transport problem for slug injection. Differential analysis is used to analyze uncertainty propagation, which is described by the variance and mean. The uncertainties of linear velocity and hydrodynamic dispersion coefficient are, respectively, characterized by the second-power and fourth-power of the length scale multiplied by a lumped relationship of variance and covariance of system parameters, i.e. the Peclet number and arrival time of maximum concentration. To validate the applicability for evaluating variance propagation in one-dimensional solute transport, two cases using field data are presented to demonstrate how parametric uncertainty can be caught depending on the manner of sampling.