Dense Nonaqueous Phase Liquid Mass Research Articles

Virtual Site Investigation to Evaluate Conceptual Site Model Development at DNAPL‐Impacted Sites

AbstractThe development of a conceptual site model (CSM) is essential to support decision making for the investigation and remediation of contaminated sites, including sites impacted by dense nonaqueous phase liquids (DNAPLs). Dynamic investigation strategies using high‐resolution site investigation tools can be used to increase the accuracy, and increase the precision (reduce the uncertainty) of a CSM, while balancing life‐cycle costs. However, the evaluation of CSM accuracy is limited by the hydrogeological and biogeochemical complexities inherent in subsurface systems. This study simulated DNAPL migration, dissolution, and reactive transport to create three high‐resolution “virtual sites” composed of 0.4–1 billion parameter values each, which were investigated by teams of leading practitioners. Use of these virtual sites allowed key hydrogeological and biogeochemical parameters to be known by the model developers but not the investigation teams. Comparison of the CSMs developed by these practitioners to the simulated values across multiple metrics (e.g., dissolved concentrations, DNAPL mass, and mass discharge) showed that 92% of those metrics were estimated within a factor of 10 and 63% were within a factor of 3 of the true (simulated) values. Furthermore, estimates of dissolved phase plume footprint were often more accurate than estimates of DNAPL source footprint, and the approaches used for investigation and data analysis were both important for CSM development. Overall, none of the site investigation approaches used to develop the CSMs resulted in the highest accuracy for all metrics, which demonstrates the need to establish best‐practices that draw from multiple approaches and vary depending on investigation objectives.

Influence of distribution characteristics of residual DNAPL on mass transfer in porous media under ethanol co-solvent flushing

The remediation of residual dense non-aqueous phase liquid (DNAPL) enhanced by co-solvents or surfactants has been investigated in many studies. Nevertheless, the influences of the residual DNAPL distribution characteristics in a porous medium, and the concentrations of the co-solvents or surfactants on the mass transfer rate of DNAPL remain relatively unexplored. For this reason, existing empirical models neglect the effects of the heterogeneity in the distribution of residual DNAPL, and the compositions of flushing floods on the DNAPL mass transfer rate. In this work, a two-dimensional micro-model is used to quantify the lumped mass transfer rate coefficients of PCE. Results show that increasing the injection rate and the ethanol concentration of flushing floods improves the mass transfer rate of PCE. Moreover, this micro-model allows for accurate quantification of variations in morphological characteristics of PCE blobs. The relative standard deviation σ of residual PCE saturation, as an indicator of morphological characteristics of PCE blobs, varies with decreasing saturation. Standard saturation S0 is used to represent the heterogeneity of residual PCE distribution. The more heterogeneous the PCE distribution, the larger the S0, and the slower the mass transfer rate. According to the variation of relative standard deviation σ with saturation, the PCE dissolution process can be divided into three stages, where the strong convection, weak convection, and diffusion within a limited distance are the primary controlling mechanisms for PCE mass transfer, respectively. Based on our study, a new empirical model, considering the distribution characteristics of residual PCE and the ethanol concentrations, is proposed to predict the PCE mass transfer process dominated by different mass transfer mechanisms in different dissolution stages.

Mapping and Monitoring of DNAPL Source Zones With Combined Direct Current Resistivity and Induced Polarization: A Field‐Scale Numerical Investigation

AbstractDirect current (DC) resistivity has been widely investigated for non‐invasive mapping of dense non‐aqueous phase liquids (DNAPLs); however, due to its difficulty in distinguishing DNAPLs from adjacent soils, the DC method is limited for static detection of DNAPLs and more often employed for monitoring DNAPL changes over time. Time‐domain induced polarization (IP) can provide complementary information to better discriminate between DNAPL, water and surrounding soils. Since highly resistive DNAPLs tend to laterally spread and pool on polarizable (chargeable) clay lenses, combined DC and IP (DCIP) has the potential to enhance static detection, and also monitoring of DNAPL source zones (SZs). The objective of this study is to assess DCIP for characterizing and monitoring DNAPL SZs at the field‐scale. A new DNAPL‐DCIP numerical model was first developed that couples a 3D multiphase flow model, which simulates DNAPL release and remediation scenarios, with a 3D DCIP model, which calculates the corresponding resistivity and chargeability response. The sensitivity of the DCIP response to key DNAPL and soil properties was then analyzed at a single subsurface location, closely matching previous theoretical and experimental observations. Finally, a field‐scale simulation of DNAPL release and remediation was conducted, with simultaneous mapping by DCIP surveys. Results demonstrate that chargeability can provide enhanced understanding of the lithological distribution that controls the variability in the DNAPL SZ, with time‐lapse resistivity being used to monitor DNAPL mass changes during SZ remediation. This numerical study suggests that combined DCIP can be valuable for site characterization and time‐lapse monitoring performance at DNAPL‐impacted sites.

Pore network and Darcy scale modelling of DNAPL remediation using ethanol flushing: Study of physical properties in DNAPL remediation

Co-solvent flushing into contaminated soils is one of the most effective techniques for Dense Non-Aqueous Phase Liquid (DNAPL) remediation. In addition to the increase of DNAPL solubility, co-solvents (e.g. ethanol) can alter the viscosity and density of aqueous phase and diffusion coefficient of solute. Any changes in these parameters can change the flow behaviour and alter the upscaled DNAPL mass transfer coefficient which is a key parameter controlling soil and groundwater remediation at Darcy-scale. While numerous studies have investigated DNAPL remediation using co-solvents at the Darcy scale, pore-scale modelling of co-solvent enhanced DNAPL remediation has not been well investigated. In this work, a three-dimensional pore-network model was developed to simulate the 1,2-dichlorobenzene (DCB) remediation experiments using ethanol-water flushing solution. The model simulates the effect of changes in solubility, viscosity, density, and diffusion coefficient during co-solvent flushing of the DNAPL. The results of pore network modelling for ethanol-water flushing for the DCB remediation were also validated using the experimental data. In addition to pore-scale modelling, a continuum scale modelling (Darcy-scale) was used for the DCB remediation using ethanol-water flushing. The results of both pore network and continuum scale modelling demonstrated that the ethanol content and flushing velocity influence the interphase mass transfer and DNAPL dissolution process. The results indicated while the mass transfer coefficient decreased in the presence of ethanol, the process of NAPL remediation was improved due to the substantial increase of solubility in the presence of co-solvent. The large scale modelling showed that NAPL bank can be formed in the front of ethanol-water mixture flushing.

Integrating deep learning-based data assimilation and hydrogeophysical data for improved monitoring of DNAPL source zones during remediation

Data assimilation techniques allow the integration of multi-source data with physical modeling of dense nonaqueous phase liquid (DNAPL) source zones to monitor their evolution in time and thereby improve remediation efforts. The DNAPL source zone is governed by multiphase physics and its architecture is usually highly irregular and nonstationary. Traditional data assimilation methods use stationary models to describe these nonstationary DNAPL saturation fields, leading to significant errors in the estimation of unknown source zone architectures (SZAs). In this study, we propose a geostatistical data assimilation method to improve performance monitoring of DNAPL remediation. We estimate the DNAPL SZA after parameterizing the DNAPL saturation field using a deep learning method instead of a stationary statistical model. First, we train a convolutional variational autoencoder (CVAE) network to capture the physics of DNAPL infiltration and depletion. Then, we incorporate the CVAE network within the Ensemble Kalman filter (EnKF) to resolve the evolving DNAPL SZA by assimilating time-lapse hydrogeophysical measurements (i.e., oscillatory hydraulic tomography, downgradient dissolved DNAPL concentration, and electrical resistivity tomography). To assess the proposed CVAE-EnKF framework's performance, we conducted numerical experiments with evolving DNAPL SZAs in a 2D heterogeneous aquifer. Results show that the proposed framework significantly improved DNAPL saturation estimates throughout the source zone over time, compared to the standard EnKF method. CVAE-EnKF reduced the estimation error of DNAPL mass remediated by 51% from EnKF, along with better predictions of source zone longevity. It also better captured the morphology and center/spread of mass of the evolving remediated portions of the source zone and provided better estimates of pooled-DNAPL mass. Furthermore, the CVAE-EnKF method is more stable and converges faster than EnKF alone. Overall, the proposed data assimilation framework can improve real-time monitoring of DNAPL remediation and risk analysis.

Experimental and Numerical Modeling of DNAPL Mass Discharge from the Elliptic Pool in Saturated Homogeneous Sandy Soil

"The present study aims to study the dissolution and mass transport of trichloroethylene (TCE) as Dense Non Aqueous Phase Liquid (DNAPL) in saturated porous media." A rectangular Perspex tank of internal dimensions (150cm length 20cm width and 40 cm height) used to represent the model aquifer. The tank was packed with homogenous soil (Karbala sand)"."Unidirectional flow at five different interstitial velocities (0.9, 1.8, 2.34, 2.7, and 3.6) cm/hr assumed to study the process. The average mass transfer coefficient" was determined for each velocity .Their values were increased with increasing the velocity reaching a limit value" .A conservative tracer is used to obtain the longitudinal and transverse aquifer dispersivities"."An elliptic shape of (TCE) pool was used to carry out the dissolution processes. Steady state dissolved (TCE) concentrations at downstream were collected from ten ports with two different depths under five interstitial velocities". Two linear relationships are created from an elliptic trichloroethylene pool: these relationships were between the average Peclet number in x-direction (Pe*x(e)) with the overall Sherwood number (Sh*(e )), and the other between the average Peclet number in y-direction (Pe*y(e) ) with the overall Sherwood number (Sh*(e))". A numerical modeling was achieved using COMSOL software.

Bioaugmentation in a Well‐Characterized Fractured Rock DNAPL Source Area

AbstractA field demonstration was performed at Edwards Air Force Base to assess bioaugmentation for treatment of a well‐characterized tetrachloroethene (PCE) dense nonaqueous phase liquid (DNAPL) source area in fractured rock. Groundwater recirculation was employed to deliver remedial amendments, including bacteria, to facilitate reductive dechlorination and enhance DNAPL dissolution. An active treatment period of 9 months was followed by a 10‐month posttreatment rebound evaluation. Dechlorination daughter products were observed in both the shallow and deep fracture zones following treatment. In the shallow fracture zone, the calculated DNAPL mass removed was approximately equal to the DNAPL mass estimated using partitioning tracer testing, and no rebound in chlorinated ethenes or ethene was observed during the posttreatment period. A maximum DNAPL dissolution enhancement factor of 5 was observed in the shallow fracture zone. In the deep fracture zone, only approximately 45% of the DNAPL mass—as estimated via partitioning tracer testing—was removed and rebound in the total molar chlorinated ethenes + ethene was observed. The difference in behavior between the shallow and deep fracture zones was attributed to DNAPL architecture and the fracture flow field.

Assessing the joint impact of DNAPL source-zone behavior and degradation products on the probabilistic characterization of human health risk

The release of industrial contaminants into the subsurface has led to a rapid degradation of groundwater resources. Contamination caused by Dense Non-Aqueous Phase Liquids (DNAPLs) is particularly severe owing to their limited solubility, slow dissolution and in many cases high toxicity. A greater insight into how the DNAPL source zone behavior and the contaminant release towards the aquifer impact human health risk is crucial for an appropriate risk management. Risk analysis is further complicated by the uncertainty in aquifer properties and contaminant conditions. This study focuses on the impact of the DNAPL release mode on the human health risk propagation along the aquifer under uncertain conditions. Contaminant concentrations released from the source zone are described using a screening approach with a set of parameters representing several scenarios of DNAPL architecture. The uncertainty in the hydraulic properties is systematically accounted for by high-resolution Monte Carlo simulations. We simulate the release and the transport of the chlorinated solvent perchloroethylene and its carcinogenic degradation products in randomly heterogeneous porous media. The human health risk posed by the chemical mixture of these contaminants is characterized by the low-order statistics and the probability density function of common risk metrics. We show that the zone of high risk (hot spot) is independent of the DNAPL mass release mode, and that the risk amplitude is mostly controlled by heterogeneities and by the source zone architecture. The risk is lower and less uncertain when the source zone is formed mostly by ganglia than by pools. We also illustrate how the source zone efficiency (intensity of the water flux crossing the source zone) affects the risk posed by an exposure to the chemical mixture. Results display that high source zone efficiencies are counter-intuitively beneficial, decreasing the risk because of a reduction in the time available for the production of the highly toxic subspecies.

Development and application of a screening model for evaluating bioenhanced dissolution in DNAPL source zones

In-situ bioremediation, a widely applied treatment technology for source zones contaminated with dense non-aqueous phase liquids (DNAPLs), has proven economical and reasonably efficient for long-term management of contaminated sites. Successful application of this remedial technology, however, requires an understanding of the complex interaction of transport, mass transfer, and biotransformation processes. The bioenhancement factor, which represents the ratio of DNAPL mass transfer under microbially active conditions to that which would occur under abiotic conditions, is commonly used to quantify the effectiveness of a particular bioremediation remedy. To date, little research has been directed towards the development and validation of methods to predict bioenhancement factors under conditions representative of real sites. This work extends an existing, first-order, bioenhancement factor expression to systems with zero-order and Monod kinetics, representative of many source-zone scenarios. The utility of this model for predicting the bioenhancement factor for previously published laboratory and field experiments is evaluated. This evaluation demonstrates the applicability of these simple bioenhancement factors for preliminary experimental design and analysis, and for assessment of dissolution enhancement in ganglia-contaminated source zones. For ease of application, a set of nomographs is presented that graphically depicts the dependence of bioenhancement factor on physicochemical properties. Application of these nomographs is illustrated using data from a well-documented field site. Results suggest that this approach can successfully capture field-scale, as well as column-scale, behavior. Sensitivity analyses reveal that bioenhanced dissolution will critically depend on in-situ biomass concentrations.

On the upscaling of mass transfer rate expressions for interpretation of source zone partitioning tracer tests

AbstractAnalysis of partitioning tracer tests conducted in dense nonaqueous phase liquid (DNAPL) source zones relies on conceptual models that describe mass exchange between the DNAPL and aqueous phases. Such analysis, however, is complicated by the complex distribution of entrapped DNAPL mass and formation heterogeneity. Due to parameter uncertainty in heterogeneous regions and the desire to reduce model complexity, the effect of mass transfer limitations is often neglected, and an equilibrium‐based model is typically used to interpret test results. This work explores the consequences of that simplifying assumption on test data interpretation and develops an alternative upscaled modeling approach to quantify effective mass transfer rates. To this end, a series of partitioning tracer tests is numerically simulated in heterogeneous two‐dimensional PCE‐DNAPL source zones, representative of a range of hydraulic conductivity and DNAPL mass distribution characteristics. The effective mass transfer coefficient corresponding to each test is determined by fitting an upscaled model to the simulated data, and regression analysis is performed to explore the correlation between various source zone metrics and the effective mass transfer coefficient. Results suggest that vertical DNAPL spreading, Reynolds number, pool fraction, and the effective organic phase saturation are the most significant parameters controlling tracer partitioning rates. Finally, a correlation for prediction of the effective (upscaled) mass transfer coefficient is proposed and verified using existing experimental data. The developed upscaled model incorporates the influence of physical heterogeneity on the rate of tracer partitioning and, thus, can be used for the estimation of source zone mass distribution characteristics from tracer test results.

Tomography-measured Spatial Distributions of Non-Aqueous Phase Liquids in Porous Media

Abstract Challenges with transport of dense non-aqueous phase liquids (DNAPLs) in geomedia have been observed by scientists and engineers. Detection of residual amounts of dense non-aqueous phase liquids in porous earth materials is important to understand the extent of contamination at sites where these materials have been released. The objectives of this study were to develop and test x-ray computed tomography (CT) methods for detection of DNAPL mass in sand cores. Two methods were used to assess the mass balance of trichloroethane (TCA) injected into selected samples. These methods included the spatial distribution method (SDM) which determined the mass from the point of injection and the mass frequency distribution method (MFDM) which used noise correction algorithms. Results showed that these methods can be used to detect the distribution of DNAPL in sand cores. Methods to assess the effective energy of the CT scanner are critical in obtaining accurate information. This study indicates that the scanning methods generally agree with the mass of DNAPL injected.

Improved time-lapse electrical resistivity tomography monitoring of dense non-aqueous phase liquids with surface-to-horizontal borehole arrays

Electrical resistivity tomography (ERT) has long-standing potential to improve characterization of sites contaminated with dense non-aqueous phase liquids (DNAPLs). However, ERT is rarely used at DNAPL sites due to the complexity of the DNAPL target coupled with the inherent limitations of traditional (surface and cross-hole) ERT configurations. Horizontal boreholes are being increasingly used in remedial strategies at contaminated field sites. This paper presents a novel surface-to-horizontal borehole (S2HB) ERT configuration for DNAPL site investigations. This array configuration is combined with four-dimensional (4D) inversion methods (applied on two-dimensional (2D) time-lapse monitoring datasets) to explore the potential benefit of S2HB ERT for mapping the spatial and temporal evolution of DNAPL mass during remediation. A field scale DNAPL remediation scenario was first simulated by a coupled DNAPL-ERT model. This demonstrated that S2HB ERT may provide significant improvements over surface ERT, particularly for delineating DNAPL mass removal at depth. A laboratory experiment was then performed to validate the S2HB ERT approach in a physical system. The experiment confirmed that 4D S2HB ERT provides improved time-lapse monitoring of NAPL changes. Confidence in the ERT responses obtained from the experiment was increased by direct comparison to the actual distribution of NAPL mapped by excavation. Independent simulation of the experiment with the DNAPL-ERT model demonstrated that the model is reliable for simulating real systems. This initial study demonstrates significantly improved resistivity imaging with surface-to-horizontal borehole ERT and its potential as a non-destructive site characterization tool for mapping DNAPL mass changes during remediation.

Architecture, persistence and dissolution of a 20 to 45 year old trichloroethene DNAPL source zone

A detailed field-scale investigation of processes controlling the architecture, persistence and dissolution of a 20 to 45year old trichloroethene (TCE) dense non-aqueous phase liquid (DNAPL) source zone located within a heterogeneous sand/gravel aquifer at a UK industrial site is presented. The source zone was partially enclosed by a 3-sided cell that allowed detailed longitudinal/fence transect monitoring along/across a controlled streamtube of flow induced by an extraction well positioned at the cell closed end. Integrated analysis of high-resolution DNAPL saturation (Sn) (from cores), dissolved-phase plume concentration (from multilevel samplers), tracer test and permeability datasets was undertaken. DNAPL architecture was determined from soil concentration data using partitioning calculations. DNAPL threshold soil concentrations and low Sn values calculated were sensitive to sorption assumptions. An outcome of this was the uncertainty in demarcation of secondary source zone diffused and sorbed mass that is distinct from trace amounts of low Sn DNAPL mass. The majority of source mass occurred within discrete lenses or pools of DNAPL associated with low permeability geological units. High residual saturation (Sn>10–20%) and pools (Sn>20%) together accounted for almost 40% of the DNAPL mass, but only 3% of the sampled source volume. High-saturation DNAPL lenses/pools were supported by lower permeability layers, but with DNAPL still primarily present within slightly more permeable overlying units. These lenses/pools exhibited approximately linearly declining Sn profiles with increasing elevation ascribed to preferential dissolution of the uppermost DNAPL. Bi-component partitioning calculations on soil samples confirmed that the dechlorination product cDCE (cis-dichloroethene) was accumulating in the TCE DNAPL. Estimated cDCE mole fractions in the DNAPL increased towards the DNAPL interface with the uppermost mole fraction of 0.04 comparable to literature laboratory data. DNAPL dissolution yielded heterogeneous dissolved-phase plumes of TCE and its dechlorination products that exhibited orders of magnitude local concentration variation. TCE solubility concentrations were relatively localised, but coincident with high saturation DNAPL lens source areas. Biotic dechlorination in the source zone area, however, caused cDCE to be the dominant dissolved-phase plume. The conservative tracer test usefully confirmed the continuity of a permeable gravel unit at depth through the source zone. Although this unit offered significant opportunity for DNAPL bypassing and decreased timeframes for dechlorination, it still transmitted a significant proportion of the contaminant flux. This was attributed to dissolution of DNAPL–mudstone aquitard associated sources at the base of the continuous gravel as well as contaminated groundwater from surrounding less permeable sand and gravel horizons draining into this permeable conduit. The cell extraction well provided an integrated metric of source zone dissolution yielding a mean concentration of around 45% TCE solubility (taking into account dechlorination) that was equivalent to a DNAPL mass removal rate of 0.4tonnes per annum over a 16m2 cell cross sectional area of flow. This is a significant flux considering the source age and observed occurrence of much of the source mass within discrete lenses/pools. We advocate the need for further detailed field-scale studies on old DNAPL source zones that better resolve persistent pool/lens features and are of prolonged duration to assess the ageing of source zones. Such studies would further underpin the application of more surgical remediation technologies.

DNAPL Source Depletion: 2. Attainable Goals and Cost-Benefit Analyses

It is difficult to quantify the range in source strength reduction (MdR) that may be attainable from in situ remediation of a dense nonaqueous-phase liquid (DNAPL) site given that available studies typically report only the median MdR without providing insights into site complexity, which is often a governing factor. An empirical study of the performance of in situ remediation at a wide range of DNAPL-contaminated sites determined MdRs for in situ bioremediation (EISB), in situ chemical oxidation (ISCO), and thermal treatment remedies. Median MdR, geometric mean MdR, and lower/upper 95 percent confidence interval for the mean were: 49x, 105x, 20x/556x, respectively, for EISB; 9x, 21x, and 4x/110x for ISCO; and 19x, 31x, and 6x/150x for thermal treatment. Lower MdR values were determined for large, complex sites and for sites with DNAPL pool-dominated source zones. A feasibility analysis of partial DNAPL depletion is described for a pool-dominated source zone. Back-diffusion from low-hydraulic conductivity units within a pool-dominated source zone is shown to potentially sustain a secondary source for more than 1,000 years, indicating that aggressive source treatment may not reduce the remediation timeframe. Estimated plume response demonstrates there may be no reduction in cost associated with aggressive treatment, and little difference in risk reduction associated with the various alternatives. Monitored natural attenuation (MNA) for the source zone is shown to be a reasonable alternative for the pool-dominated source zone considered in this example. It is demonstrated that pool-dominated source zones with a large range in initial DNAPL mass (250 to 1,500 kg) may correspond to a narrow range in source strength (20 to 30 kg/year). This demonstrates that measured source strength is nonunique with respect to DNAPL mass in the subsurface and, thus, source strength should not be used as the sole basis for predicting how much DNAPL mass remains or must be removed to achieve a target goal. If aggressive source zone treatment is to be implemented due to regulatory requirements, strategic pump-and-treat is shown to be most cost effective. These remedial decisions are shown to be insensitive to a range of possible DNAPL pool conditions. At sites with an existing pump-and-treat system, a significant increase in mass removal and source strength reduction may be achieved for a low incremental cost by strategic placement of extraction wells and pumping rate selection. © 2014 Wiley Periodicals, Inc.

Evaluating four-dimensional time-lapse electrical resistivity tomography for monitoring DNAPL source zone remediation

Practical, non-invasive tools do not currently exist for mapping the remediation of dense non-aqueous phase liquids (DNAPLs). Electrical resistivity tomography (ERT) exhibits significant potential but has not yet become a practitioner's tool due to challenges in interpreting the survey results at real sites. This study explores the effectiveness of recently developed four-dimensional (4D, i.e., 3D space plus time) time-lapse surface ERT to monitor DNAPL source zone remediation. A laboratory experiment demonstrated the approach for mapping a changing NAPL distribution over time. A recently developed DNAPL-ERT numerical model was then employed to independently simulate the experiment, providing confidence that the DNAPL-ERT model is a reliable tool for simulating real systems. The numerical model was then used to evaluate the potential for this approach at the field scale. Four DNAPL source zones, exhibiting a range of complexity, were initially simulated, followed by modeled time-lapse ERT monitoring of complete DNAPL remediation by enhanced dissolution. 4D ERT inversion provided estimates of the regions of the source zone experiencing mass reduction with time. Results show that 4D time-lapse ERT has significant potential to map both the outline and the center of mass of the evolving treated portion of the source zone to within a few meters in each direction. In addition, the technique can provide a reasonable, albeit conservative, estimate of the DNAPL volume remediated with time: 25% underestimation in the upper 2m and up to 50% underestimation at late time between 2 and 4m depth. The technique is less reliable for identifying cleanup of DNAPL stringers outside the main DNAPL body. Overall, this study demonstrates that 4D time-lapse ERT has potential for mapping where and how quickly DNAPL mass changes in real time during site remediation.

A geometric approach to joint inversion with applications to contaminant source zone characterization

This paper presents a new joint inversion approach to shape-based inverse problems. Given two sets of data from distinct physical models, the main objective is to obtain a unified characterization of inclusions within the spatial domain of the physical properties to be reconstructed. Although our proposed method generally applies to many types of inverse problems, the main motivation here is to characterize subsurface contaminant source zones by processing down-gradient hydrological data and cross-gradient electrical resistance tomography observations. Inspired by Newton's method for multi-objective optimization, we present an iterative inversion scheme in which descent steps are chosen to simultaneously reduce both data-model misfit terms. Such an approach, however, requires solving a non-smooth convex problem at every iteration, which is computationally expensive for a pixel-based inversion over the whole domain. Instead, we employ a parametric level set technique that substantially reduces the number of underlying parameters, making the inversion computationally tractable. The performance of the technique is examined and discussed through the reconstruction of source zone architectures that are representative of dense non-aqueous phase liquid (DNAPL) contaminant release in a statistically homogenous sandy aquifer. In these examples, the geometric configuration of the DNAPL mass is considered along with additional information about its spatial variability within the contaminated zone, such as the identification of low and high saturation regions. Comparison of the reconstructions with the true DNAPL architectures highlights the superior performance of the model-based technique and joint inversion scheme.

A new coupled model for simulating the mapping of dense nonaqueous phase liquids using electrical resistivity tomography

Electrical resistivity tomography (ERT) has, for a considerable length of time, been considered promising for subsurface characterization activities at sites contaminated with dense, nonaqueous phase liquids (DNAPLs). The relatively few field studies available exhibit mixed results, and the technique has not yet become a common tool for mapping such contaminants or tracking mass reduction during their remediation. To help address this, a novel, coupled DNAPL-ERT numerical model was developed that can provide a platform for the systematic evaluation of ERT under a wide range of realistic, field-scale subsurface environments. The coupled model integrated a 3D multiphase flow model, which generates realistic DNAPL scenarios, with a 3D ERT forward model to calculate the corresponding resistivity response. Central to the coupling, and a key contribution, was a new linkage between the main hydrogeologic parameters (including hydraulic permeability, porosity, clay content, groundwater salinity and temperature, and air, water, and DNAPL contents evolving with time) and the resulting bulk electrical resistivity by integration of a variety of published relationships. Sensitivity studies conducted for a single node compared well to published correlations and for a field-scale domain demonstrated that the model is robust and sensitive to heterogeneity in DNAPL distribution and soil structure. A field-scale simulation of a DNAPL release and its subsequent remediation, monitored by ERT surface surveys, demonstrated that ERT is promising for mapping DNAPL mass reduction. The developed model provides a cost-effective avenue to test optimum ERT data acquisition, inversion, and interpretative tools, which should assist in deploying ERT strategically at contaminated sites.

The impact of low-temperature seasonal aquifer thermal energy storage (SATES) systems on chlorinated solvent contaminated groundwater: Modeling of spreading and degradation

Groundwater systems are increasingly used for seasonal aquifer thermal energy storage (SATES) for periodic heating and cooling of buildings. Its use is hampered in contaminated aquifers because of the potential environmental risks associated with the spreading of contaminated groundwater, but positive side effects, such as enhanced contaminant remediation, might also occur. A first reactive transport study is presented to assess the effect of SATES on the fate of chlorinated solvents by means of scenario modeling, with emphasis on the effects of transient SATES pumping and applicable kinetic degradation regime. Temperature effects on physical, chemical, and biological reactions were excluded as calculations and initial simulations showed that the small temperature range commonly involved (ΔT<15 °C) only caused minor effects. The results show that a significant decrease of the contaminant mass and (eventually) plume volume occurs when degradation is described as sediment-limited with a constant rate in space and time, provided that dense non-aqueous phase liquid (DNAPL) is absent. However, in the presence of DNAPL dissolution, particularly when the dissolved contaminant reaches SATES wells, a considerably larger contaminant plume is created, depending on the balance between DNAPL dissolution and mass removal by degradation. Under conditions where degradation is contaminant-limited and degradation rates depend on contaminant concentrations in the aquifer, a SATES system does not result in enhanced remediation of a contaminant plume. Although field data are lacking and existing regulatory constraints do not yet permit the application of SATES in contaminated aquifers, reactive transport modeling provides a means of assessing the risks of SATES application in contaminated aquifers. The results from this study are considered to be a first step in identifying the subsurface conditions under which SATES can be applied in a safe or even beneficial manner.

The use of mass depletion–mass flux reduction relationships during pumping to determine source zone mass of a reactive brominated-solvent DNAPL

Mass depletion-mass flux relationships usually applied to a groundwater plume were established at field scale for groundwater pumped from within the source zone of a dense non-aqueous phase liquid (DNAPL). These were used as part of multiple lines of evidence in establishing the DNAPL source mass and architecture. Simplified source mass-dissolved concentration models including those described by exponential, power, and error functions as well as a rational mass equation based on the equilibrium stream tube approach were fitted to data from 285 days of source zone pumping (SZP) from a single well which removed 152 kg of dissolved organics from a multi-component, reactive brominated solvent DNAPL. The total molar concentration of the source compound, tetrabromoethane and its daughter products was used as a single measure of contaminant concentration to relate to source mass. A partitioning inter-well tracer test (PITT) conducted prior to the SZP provided estimates of groundwater travel times, enabling parameterisation of the models. After accounting for capture of the down-gradient dissolved plume, all models provided a good fit to the observed data. It was shown that differentiation between models would only emerge after appreciably more pumping from the source zone. The model fits were not particularly sensitive to the exponent parameters and variance of groundwater travel time. In addition, the multi-component nature of the DNAPL did not seem to affect the utility of the models for the period examined. Estimates of the DNAPL mass prior to the start of SZP from the models were greatest where the log of the variance of travel time was used explicitly in the source depletion models (mean 295kg) compared to where the associated power exponent and variance was fitted freely (mean 258 kg). The estimates of source mass were close to that of 220kg determined from the PITT. In addition to the PITT, multi-level groundwater sampling from within the source zone provided important supporting information for developing the conceptual model of the source zone. It is concluded that SZP may be an effective and relatively simple means for characterising DNAPL source zones.

Experimental Study of the Effects of DNAPL Distribution on Mass Rebound

The release of stored dissolved contaminants from low permeability zones contributes to plume persistence beyond the time when dense nonaqueous phase liquid (DNAPL) has completely dissolved. This is fundamental to successfully meeting acceptable low concentrations in groundwater that are driven by site-specific cleanup goals. The study goals were to assess the role of DNAPL entrapment morphology on mass storage and plume longevity. As controlled field studies are not feasible, two-dimensional (2D) test tanks were used to quantify the significance of mass loading processes from source dissolution and stored mass rebound. A simple two-layer soil domain representing a high permeable formation sand overlying a zone of lower permeability sand was used in the tests. DNAPL mass depletion through dissolution was monitored via X-ray photon attenuation, and effluent samples were used to monitor the plume. These data enabled analysis of the DNAPL distribution, the dissolved plume, and the dissolved phase distribution within the low permeability layer. Tests in an intermediate tank showed that mass storage contributes substantially to plume longevity. Detectable effluent concentrations persisted long after DNAPL depletion. The small tank results indicated that the DNAPL morphology influenced the flow field and caused distinctive transport mechanisms contributing to mass storage. Zones of high DNAPL saturation at the interface between the low and high permeability layers exhibited flow bypassing and diffusion dominated transport into the low permeability layer. In the absence of a highly saturated DNAPL zone near the soil interface the contaminant penetrated deeper into the low permeability layer caused by a combination of advection and diffusion.