Dense Non-aqueous Phase Liquid Contaminants Research Articles

Bayesian hybrid-kernel machine-learning-assisted sensitivity analysis and sensitivity-relevant inverse modeling for groundwater DNAPL contamination

Accurate source characterization and transport parameter estimation is important when seeking to predict the spatiotemporal distribution of dense non-aqueous phase liquid (DNAPL) contaminants in groundwater. However, this is a complex multimodal search problem prone to equifinality and premature convergence, which leads to considerable error. To address this, a sensitivity-relevant dynamic swarm intelligence (SRD-SI) algorithm embedded in a homotopy-variation mechanism is proposed in the present study to rationally balance the inversion processes of sensitivity-varied source characteristics and DNAPL transport parameters. In this approach, global optima are progressively approached in conjunction with the homotopy variation of the search space. Furthermore, to avoid computationally expensive numerical model repetition during the sensitivity analysis and inverse iterations, a Bayesian-based optimization framework that combines multiple kernel functions in a kernel extreme learning machine (KELM) model is designed considering the complex site conditions and statistical characteristics of the input variables, thus creating the Bayesian hybrid KELM (BHK-ELM) model for the reliable surrogate modeling of numerical DNAPL-transport simulations. The results show that the BHK-ELM model recognizes and effectively reconstructs the complex input − output mapping of the numerical model by increasing the determination coefficient R2 to 0.9988 while improving the computational efficiency approximately 4500-fold. Because source characteristics and boundary conditions are far more sensitive than transport parameters to the contaminant distribution, conventional inverse modeling methods struggle to accurately identify these transport parameters. In contrast, the proposed inverse modeling system combining sensitivity analysis, swarm intelligence, and homotopy variation is more stable and provides significantly more accurate estimations for all unknown variables. Compared with the traditional SI algorithm, the homotopy-variation SRD-SI reduced the maximum inversion relative error from 46.22 % to 9.53 %, while the mean inversion relative error was reduced from 11.09 % to 3.90 %.

The effect of Tween 80 on monochlorobenzene migration in bentonite

Several studies conducted at industrial sites have documented the infiltration of dense non-aqueous phase liquids (DNAPLs) into clay layers, a phenomenon potentially influenced by the coexistence of chemicals like surfactants in some common pollutants. Bentonite (Ben), monochlorobenzene (MCB), and Tween 80 (T80) were selected as reference components to investigate the influences of nonionic surfactants on DNAPLs migration in clays. Results showed that T80 promotes MCB dissolution and encourages MCB adsorption on Ben. This process reduces the hydrophilicity of Ben, resulting in water loss and shrinkage, which creates cracks and facilitates the migration of MCB within the clay. Tw80 notably enhances MCB solubility, as indicated by a molar solubilization ratio of 7.80. The MCB adsorption on Ben (QMCB) displays a linear increase with raising the T80 adsorption on Ben (QT80), especially when QT80 are below the thresholds, e.g., 408.4 mg/g at pH 3 and 339.3 mg/g at pH 7; however, QMCB is decreased with increasing adsorbed T80 further. The average fracture ratio, crack length, and crack width of cracked samples in the cracking experiments were 0.794%, 11.29 mm, and 0.209 mm, respectively. The findings here contribute to understanding the role of surfactants in VOC transport in contaminated sites.

Rock core VOC profiles diagnostic of aquitard occurrence and integrity in a multi-layered sedimentary rock aquifer flow system

Aquitard assessment poses a challenge for practitioners and researchers managing dense non-aqueous phase liquid (DNAPL) contaminants in sedimentary rock aquifer systems. Within these systems, DNAPL migration and bulk hydraulic properties are controlled by fracture networks which are difficult to characterize at relevant scales with conventional methods. A previous study at a DNAPL contaminated site used contrasts in high-resolution vertical gradients to delineate four aquitards and two surfaces with poor vertical connectivity within a thick (>200 m) sedimentary rock aquifer system primarily composed of layered sandstones. In this study, we corroborate that method by using the existing DNAPL contamination as a tracer to identify and characterize the aquitards in the sequence and assess aquitard integrity. Closely spaced samples of rock from four continuous cores were collected and analyzed for volatile organic compounds (VOCs). The cores were collected along a transect perpendicular to groundwater flow and 75 m downgradient of the DNAPL source zone. Dissolved phase contaminant concentrations were collected using high-resolution multilevel systems placed along the plume centerline, downgradient from the source. The rock core and groundwater VOC concentration profiles suggest a primary aquitard limits vertical migration of both DNAPL and the associated dissolved phase contaminants, despite relatively large, downward gradients across its lower boundary. A calibrated, three-dimensional numerical groundwater flow model indicates an anisotropy factor of 1,000 for this aquitard. The Kv values for all four aquitards are only slightly lower than the values for the aquifers. However, the aquitard Kv values are 1–3 orders of magnitude less than their Kh values, and the aquitard Kh values are often similar to or even greater than the Kh values for the aquifers. Therefore, large anisotropy, rather than exceptionally low Kv values, distinguish the aquitards from the aquifers in this system. Fracture network characterization of nearby outcrops showed the anisotropy of the aquitards can be attributed to laterally extensive, bedding parallel partings coupled with short, frequently terminating, and poorly connected vertical fractures. In addition, the rock VOC profiles combined with fracture network data show that fracture termination surfaces can be powerful inhibitors of downward DNAPL migration providing additional evidence for the importance of these features in sedimentary rock flow systems. Ultimately, this study reveals the important influence of anisotropic aquitards on DNAPL migration, accumulation, and persistence, as well as associated plume migration. Furthermore, it demonstrates that subtle contrasts critical to aquitard integrity may be easily missed with long screened wells and other conventional, low resolution site characterization methods.

A Case Study of Deep DNAPL Contamination in Marine Soft Clays

Aquifers in China’s southeast coastal areas are protected by the overlying marine soft clays formed in Holocene transgression. However, a fundamental understanding of the characteristics of DNAPL (dense nonaqueous phase liquid) contamination in marine soft clays is limited. The study was conducted on the site of a former pharmaceutical factory in Shanghai, where serious 1,1,2-trichloroethane (DNAPL) contamination was detected up to the depth of 22.0 m below the existing grade. Partitioning calculation method was used to identify the presence of pure phase, and the results showed that pure 1,1,2-trichloroethane was accumulated at the interface of the upper soft silty clay and lower soft clay. The vertical transport was believed to be the pure DNAPL displacing pore water following the principle of two-phase flow, rather than the convection and diffusion of aqueous phase. The contamination (NAPL-soil interaction) impacted the soil properties slightly, and this effect could not account for the deep contamination. Soil structure analysis showed that these clays contained a proportion of large interaggregate pores, providing pathways for the transport of pure DNAPL. Considering their flocculated structure, the marine soft clays are not capable to perform as a barrier to prevent the downward migration of pure DNAPL.

A combined search method based on a deep learning combined surrogate model for groundwater DNAPL contamination source identification

Ensemble Kalman filter (EnKF) and optimization methods are two mainstream methods in groundwater contamination source identification, but most researchers usually only use or improve on one method. However, each method has strengths and weaknesses, and using one method alone may cause inaccuracy of the identification results for complex situations. Therefore, it is necessary to explore the combination of methods. In this paper, for the optimization method, to further enhance the solution precision of the optimization model for groundwater dense non-aqueous phase liquid (DNAPL) contamination source identification (GDCSI), we first constructed an improved butterfly optimization algorithm by introducing the dynamic switching probability mechanism in the previous butterfly optimization algorithm. Next, the EnKF method and optimization method (based on the improved butterfly optimization algorithm) were used respectively for GDCSI, to assess the strengths and weaknesses of the methods. Then, according to the strengths and weaknesses of the EnKF and optimization methods, the two methods were merged to build a more robust and practical combined search method (CSM) for GDCSI, to further enhance the identification accuracy and effectiveness. In addition, we innovatively applied the EnKF method to combine two single deep learning surrogate models: the deep belief neural network surrogate model and the deep residual neural network surrogate model. And a deep learning combined surrogate model was established, which further enhanced the approximation precision and applicability to the groundwater DNAPL contamination multiphase flow numerical simulation model. Finally, the results of CSM were compared with those of two single methods to analyze the former's effectiveness. The results showed that the CSM significantly improved the identification accuracy and effectiveness of GDCSI compared with any single method.

Evaluation of alkaline activated sodium persulfate sustained release rod for the removal of dissolved trichloroethylene

The presence of trichloroethylene (TCE) dense non-aqueous phase liquid (DNAPL) in the subsurface can generate a dissolved phase plume in groundwater. This study developed an alkaline activated sodium persulfate (SPS) sustained release oxidation rod (alkaline SPS SR-Rod) for long-term in situ chemical oxidation accelerated treatment of TCE dissolved from TCE DNAPL, by creating a greater concentration gradient at the TCE DNPL boundary. The dissolution of TCE DNAPL (1 mL) in water (280 mL) generated ~700 mg L−1, with a volumetric mass transfer coefficient (kLa) of 0.0187 d−1. The alkaline SPS SR-Rod system had a kLa of 0.013 d−1 for TCE dissolution at early stage, and thereafter aqueous TCE concentration remained below ~10 mg L−1 over 60 d of reaction. An SPS SR-Rod life-span of 186 d, for 90% of SPS released from the rod, was estimated. In the soil-water system, aqueous TCE was maintained < 3 mg L− 1 throughout the reaction and the soil oxidant demand was determined to be ~4 g-SPS/kg-soil in the alkaline SPS SR-Rod system. These results revealed that the use of the alkaline SPS SR-Rod can be effective as a method of treating dissolved TCE released from DNAPL contamination, and thereby accelerating TCE DNAPL removal.

Analysis of Dense Non-aqueous Phase Liquid Contaminants Effects on Soil Permeability by Response Surface Methodology

Soil contamination is considered a controversial issue in most countries. Nowadays, it is important to clearly understand how pollutants influence the soil from different sources. Today, hydrocarbons are one of the most important sources of soil contaminants, which is considered as a fundamental issue at the global level. The current study aims to analyze and model the effect of simultaneous parameters (time and concentration) of phenols and naphthalene with different percentages (10, 15, 20 and 25%) together with the amount of bentonite in fine-grained sandy soil. The designed experiments made use of response surface methodology (RSM) and Design-Expert software to carry out a computer-based simulation. According to the proposed model, the amount of bentonite is most affected by the permeability of the soil. The obtained results also showed that the permeability significantly decreases in the light of increasing the percentage of phenol and naphthalene coupled with the amount of bentonite and the age of contamination. On average, an 80% reduction of permeability was observed in contaminated soil, which was found in the soil contaminated with naphthalene. According to the results of the synergistic effects of time, the considerable impacts of both the percentage of hydrocarbon pollutants and the amount of bentonite on the reduction of permeability are quite evident.

Assessing human health risk of groundwater DNAPL contamination by quantifying the model structure uncertainty

The contamination of groundwater with dense non-aqueous phase liquids (DNAPL) can pose long-term risks to human health. Due to the complexity of geological environments and the properties of DNAPL, a key step in human health risk (HHR) assessment is the establishment of a reliable DNAPL transport model. In this study, we evaluate the impact of the model structure uncertainty on DNAPL transport modeling for HHR assessment. First, Gaussian process regression (GPR) was used to learn the structure error of the DNAPL transport model through statistical simulations, and then, Markov chain Monte Carlo (MCMC) simulation was used to calibrate the parameters of the physical model and GPR. On the basis of two case studies, namely, a sandbox experiment and a synthetic DNAPL transport model investigation, the results demonstrated that ignoring the model structure error will lead to deviations during parameter calibrations and model predictions. This is because the model parameters could be overfitted to compensate for the model structure error during the calibration process. Results of variance decomposition verified that the model structure error was the main uncertainty source in DNAPL transport modeling for both of the case studies. The DNAPL transport modeling and HHR assessment conducted by quantifying the uncertainties of the model parameters and structure simultaneously was found to be more reliable than that by calibrating only the model parameters. In addition, the HHR assessment of groundwater DNAPL contamination without considering the model structure error could lead to misleading depictions of the key risk zone. We propose that GPR is an effective technique to quantitatively describe the structure error of DNAPL transport models.

Assessing aquitard integrity in a complex aquifer – aquitard system contaminated by chlorinated hydrocarbons

This study investigates for the first time the integrity of multiple stacked aquitards with different degrees of contaminant degradation. Aquitard integrity was assessed in a contaminated, multi-layered, alluvial aquifer-aquitard system (Ferrara, northern Italy). The system was contaminated by mixed organic contaminants of industrial origin (mostly chlorinated ethenes) that were illegally disposed in an urban dump four to five decades ago. High spatial resolution profiles of hydraulic head, geochemistry and chlorinated hydrocarbon concentrations were determined through the multi-layered system via discrete interval sampling of continuous cores and multilevel groundwater sampling, at three locations aligned along a transect adjacent to the buried waste to a maximum depth of 53 m below the water table.The profiles revealed that the two shallow aquitards had low integrity with respect to impeding downward migration of dense non-aqueous phase liquid (DNAPL), and provided little protection to the underlying aquifers against DNAPL contamination due to preferential pathways through imperceptible fractures and/or permeable micro-beds. However, both aquitards inhibited downward DNAPL migration to some extent due to DNAPL retention along its flow paths and accumulation at lower permeability interfaces, with decreasing peak concentrations at the top of successively deeper aquitard units. Moreover, both aquitards enhanced contaminant biodegradation due to the occurrence of organic rich sub-layers, influencing the contaminant plume composition, mobility and fate in the underlying and overlying aquifers.The deepest aquitard showed evidence of DNAPL accumulation at the top and slow diffusion-dominated transport consistent with 40 years of transport, suggesting higher integrity compared to the two shallower aquitards. However, the occurrence of micro-fractures and/or discontinuities in the aquitard upgradient under the dump (source) is the most likely explanation for contamination of the deepest aquifer. Analytical 1-D simulations of the diffusion profiles in the deepest aquitard revealed that DNAPL contamination down to the top of this aquitard occurred with minimal delay after DNAPL waste disposal began.The results highlight the necessity of high-resolution vertical profiling for assessing the presence of imperceptible features relevant to DNAPL migration and integrity of individual aquitards affecting organic contaminant source zone mass and phase distributions over decades.

Quantification of Uncertainties from Image Processing and Analysis in Laboratory-Scale DNAPL Release Studies Evaluated by Reflective Optical Imaging

Subsurface DNAPL (dense non-aqueous phase liquid) contamination from (un-) intentional spilling typically leads to severe environmental hazards. A large number of studies have demonstrated the relevance of DNAPL source zone geometry for the determination of contaminant plume propagation in groundwater. Optical imaging represents a promising non-invasive method for identifying DNAPL saturation without disturbing multiphase flow dynamics. However, workflow and image analysis methodologies have not been sufficiently developed or described for general application to related experimental efforts. For example, the choice of dye(s) used for phase colorization affects image processing and can bias final estimations of DNAPL saturations. In this study, we perform a series of DNAPL migration and entrapment studies in transparent tanks that are filled with three different types of porous media. Different dyes are used and raw images are acquired. Subsequently, these are used to evaluate a suite of image processing and analysis approaches, which are organized into a workflow. Our approach allows for us to identify key image processing and analysis steps that introduce the most error. Applicable dye configurations led to uncertainties of up to 41% depending on the selection of processing steps. Based on these findings, it was possible to delineate a flexible framework for image processing and analysis that has the potential for transfer and application in other tank experiment setups.

The impact of water saturation on the infiltration behaviour of elemental mercury DNAPL in heterogeneous porous media

Industrial use has led to the presence of liquid elemental mercury (Hg0) worldwide in the subsurface as Dense NonAqueous Phase Liquid (DNAPL), resulting in long lasting sources of contamination, which cause harmful effects on human health and detrimental consequences on ecosystems. However, to date, insight into the infiltration behaviour of elemental mercury DNAPL is lacking. In this study, a two-stage flow container experiment of elemental mercury DNAPL infiltration into a variably water saturated stratified sand is described. During the first stage of the experiment, 16.3 ml of liquid Hg0 infiltrated and distributed into an initially partially water saturated system. Afterwards, during the second stage of the experiment, consisting of the simulation of a “rain event” to assess whether the elemental mercury already infiltrated could be mobilized due to local increases in water saturation, a significant additional infiltration of 4.7 ml of liquid mercury occurred from the remaining DNAPL source. The experiment showed that, under conditions similar to those found in the field, Hg0 DNAPL infiltration is likely to occur via fingers and is strongly controlled by porous medium structure and water saturation. Heterogeneities within the porous medium likely determined preferential pathways for liquid Hg0 infiltration and distribution, as also suggested by dual gamma ray measurements. Overall, this study highlights that the infiltration behaviour of mercury DNAPL is strongly impacted by water saturation. In the field, this may result in a preferential infiltration of Hg0 DNAPL in wetter areas or in its mobilization due to wetting during a rain event, as indicated by this study, or a groundwater table rise. This should be considered when assessing the likely distribution pathways of historic mercury DNAPL contamination as well as the remediation efforts.

Estimation of representative elementary volume for DNAPL saturation and DNAPL-water interfacial areas in 2D heterogeneous porous media

Representative elementary volume (REV) is important to determine properties of porous media and those involved in migration of contaminants especially dense nonaqueous phase liquids (DNAPLs) in subsurface environment. In this study, an experiment of long-term migration of the commonly used DNAPL, perchloroethylene (PCE), is performed in a two dimensional (2D) sandbox where several system variables including porosity, PCE saturation (Soil) and PCE-water interfacial area (AOW) are accurately quantified by light transmission techniques over the entire PCE migration process. Moreover, the REVs for these system variables are estimated by a criterion of relative gradient error (εgi) and results indicate that the frequency of minimum porosity-REV size closely follows a Gaussian distribution in the range of 2.0mm and 8.0mm. As experiment proceeds in PCE infiltration process, the frequency and cumulative frequency of both minimum Soil-REV and minimum AOW-REV sizes change their shapes from the irregular and random to the regular and smooth. When experiment comes into redistribution process, the cumulative frequency of minimum Soil-REV size reveals a linear positive correlation, while frequency of minimum AOW-REV size tends to a Gaussian distribution in the range of 2.0mm–7.0mm and appears a peak value in 13.0mm–14.0mm. Undoubtedly, this study will facilitate the quantification of REVs for materials and fluid properties in a rapid, handy and economical manner, which helps enhance our understanding of porous media and DNAPL properties at micro scale, as well as the accuracy of DNAPL contamination modeling at field-scale.

Tracing of residual multiple DNAPL sources in the subsurface using 222Rn as a natural tracer at an industrial complex in Wonju, Korea

Depth-discrete tracing of residual dense non-aqueous phase liquid (DNAPL) sources in the subsurface is of great importance in making decisions related to contaminated groundwater remediation. Temporal variations in the natural tracer 222Rn and contaminant concentrations in groundwater contaminated with multiple chlorinated contaminants, such as trichloroethene, carbon tetrachloride, and chloroform, were examined to trace residual multiple DNAPL contaminants at an industrial complex in Wonju, Korea. The 222Rn activities and multiple DNAPL concentrations in the groundwater fluctuated irregularly according to the groundwater recharge. The natural tracer 222Rn in groundwater present in the soil layer, originating from the underlying crystalline biotite granite, had a wide range from 29,000 to 179,000 Bq/m3, and total concentrations of chlorinated solvents ranged from 0.06 to 17.77 mg/l, indicating the ambiguous results of 222Rn for tracing the residual DNAPL sources. In this paper, a method is presented to locate zones with a high probability of containing depth-discrete residual multiple DNAPL sources using 222Rn and considering relative contaminant concentrations. The results demonstrate that the combination of the 222Rn activities as a natural tracer and the relative contaminant concentrations is able to be used as a useful tool for tracing residual DNAPLs.

Estimation of Electromagnetic Properties in Soil Testbeds Using Frequency and Time Domain Modeling

Contamination of underground systems causes serious detriment of the environment and can pose a serious threat to human health. The challenge of locating many common contaminants creates the need to develop technologies that enhance our ability to detect and characterize underground contamination. Cross-Well Radar (CWR) is being evaluated as a potential technology for detection of hazardous contaminants, such as Dense Non-Aqueous Phase Liquids (DNAPLs), present in underground environments. This paper addresses the development of enabling CWR technologies that rely on the use of transmission and reflection measurements to detect changes in soil electromagnetic (EM) properties caused by the presence of underground target elements, such DNAPL contamination. Time- and frequency-domain measurements and simulations are applied to assess the performance of antennas and design testbeds for proper estimation of EM properties in soil systems. Results indicate that proper development of CWR testbeds must account for wave propagation near sharp EM boundaries. Time-domain analysis shows that s-parameters measurements in a properly developed testbed can be applied to accurately estimate EM properties of bulk soil. The integrated use of soil testbeds with time- and frequency-domain EM modeling, thus, lead to enhanced CWR enabling technologies for DNAPLs detection in underground environments.

PCE dissolution and simultaneous dechlorination by nanoscale zero-valent iron particles in a DNAPL source zone

While the capability of nanoscale zero-valent iron (NZVI) to dechlorinate organic compounds in aqueous solutions has been demonstrated, the ability of NZVI to remove dense non-aqueous phase liquid (DNAPL) from source zones under flow-through conditions similar to a field scale application has not yet been thoroughly investigated. To gain insight on simultaneous DNAPL dissolution and NZVI-mediated dechlorination reactions after direct placement of NZVI into a DNAPL source zone, a combined experimental and modeling study was performed. First, a DNAPL tetrachloroethene (PCE) source zone with emplaced NZVI was built inside a small custom-made flow cell and the effluent PCE and dechlorination byproducts were monitored over time. Second, a model for rate-limited DNAPL dissolution and NZVI-mediated dechlorination of PCE to its three main reaction byproducts with a possibility for partitioning of these byproducts back into the DNAPL was formulated. The coupled processes occurring in the flow cell were simulated and analyzed using a detailed three-dimensional numerical model. It was found that subsurface emplacement of NZVI did not markedly accelerate DNAPL dissolution or the DNAPL mass-depletion rate, when NZVI at a particle concentration of 10g/L was directly emplaced in the DNAPL source zone. To react with NZVI the DNAPL PCE must first dissolve into the groundwater and the rate of dissolution controls the longevity of the DNAPL source. The modeling study further indicated that faster reacting particles would decrease aqueous contaminant concentrations but there is a limit to how much the mass removal rate can be increased by increasing the dechlorination reaction rate. To ensure reduction of aqueous contaminant concentrations, remediation of DNAPL contaminants with NZVI should include emplacement in a capture zone down-gradient of the DNAPL source.

Modeling the Effects of Microbial Competition and Hydrodynamics on the Dissolution and Detoxification of Dense Nonaqueous Phase Liquid Contaminants

The real significance and engineering potential for bioenhanced dissolution of chlorinated ethene dense nonaqueous phase liquid (DNAPL) contaminants are currently not well understood, in part because they can be influenced by a complex set of factors, including microbial competition for growth substrates. Mathematical simulations were performed to evaluate the effects of competition between Dehalococcoides ethenogenes and Desulfuromonas michiganensis for the electron acceptor tetrachloroethene (PCE) on the distribution of dehalorespirers, PCE dissolution, and the extent of PCE detoxification. The modeling results demonstrate that the outcome of competition between populations for growth substrates can have a significant impact on bioenhancement and, thus, on DNAPL source zone longevity and identify the key factors in determining the outcome of competition and its effects on DNAPL dissolution. The potential for bioenhancement is greatest at lower groundwater velocities. At higher velocities, kinetic properties play a key role in determining which population dominates and where, and the amount of bioenhancement that is realized. Engineered bioremediation techniques that maintain multiple dehalorespiring populations may offer the best approach for optimizing the twin cleanup goals of reduced source zone longevity and complete detoxification while maximizing the utilization of added electron donors.

Effects of Groundwater Velocity and Permanganate Concentration on DNAPL Mass Depletion Rates during In Situ Oxidation

In situ chemical oxidation (ISCO) using permanganate has been increasingly applied to deplete mass from dense nonaqueous-phase liquid (DNAPL) source zones. However, uncertainty in the performance of ISCO on DNAPL contaminants is partially attributable to a limited understanding of interactions between the oxidant, subsurface hydrology, and DNAPL mass transfer, resulting in failure to optimize ISCO applications. To investigate these interactions, a factorial design experiment was conducted using one-dimensional flow through tube reactors to determine how groundwater velocity, permanganate concentration, and DNAPL type affected DNAPL mass depletion rates. DNAPL mass depletion rates were found to increase with increasing groundwater velocity, or increasing oxidant concentration. An interaction occurred between the two factors, where high oxidant concentrations had little impact on mass depletion rates at high velocities. High oxidant concentration systems experienced gas generation. Mass depletion rates were fastest at high velocities, but required additional oxidant mass and pore volume addition to achieve complete mass depletion. Lower-velocity systems were more efficient with respect to oxidant mass and pore volume requirements, but mass depletion rates were reduced.

Temporal evolution of DNAPL source and contaminant flux distribution: Impacts of source mass depletion

We investigated, using model simulations, the changes occurring in the distribution of dense non-aqueous phase liquid (DNAPL) mass ( S n) within the source zone during depletion through dissolution, and the resulting changes in the contaminant flux distribution ( J) at the source control plane (CP). Two numerical codes (ISCO3D and T2VOC) were used to simulate selected scenarios of DNAPL dissolution and transport in three-dimensional, heterogeneous, spatially correlated, random permeability fields with emplaced sources. Data from the model simulations were interpreted based on population statistics (mean, standard deviation, coefficient of variation) and spatial statistics (centroid, second moments, variograms). The mean and standard deviation of the S n and J distributions decreased with source mass depletion by dissolution. The decrease in mean and standard deviation was proportional for the J distribution resulting in a constant coefficient of variation (CV), while for the S n distribution, the mean decreased faster than the standard deviation. The spatial distributions exhibited similar behavior as the population distribution, i.e., the CP flux distribution was more stable (defined by temporally constant second moments and range of variograms) than the S n distribution. These observations appeared to be independent of the heterogeneity of the permeability ( k) field (variance of the log permeability field = 1 and 2.45), correlation structure (positive vs. negative correlation between the k and S n domains) and the DNAPL dissolution model (equilibrium vs. rate-limited), for the cases studied. Analysis of data from a flux monitoring field study (Hill Air Force Base, Utah) at a DNAPL source CP before and after source remediation also revealed temporal invariance of the contaminant flux distribution. These modeling and field observations suggest that the temporal evolution of the contaminant flux distribution can be estimated if the initial distribution is known. However, the findings are preliminary and broader implications to sampling strategies for remediation performance assessment need to be evaluated in additional modeling and experimental studies.

Three‐dimensional self‐potential inversion for subsurface DNAPL contaminant detection at the Savannah River Site, South Carolina

Self‐potential (SP) data are collected over an area of approximately 250 m2 at the Department of Energy Savannah River Site where there is known subsurface dense nonaqueous phase liquid (DNAPL) contamination. Nonpolarizing electrodes are used to measure the SP signal on a two‐dimensional (2‐D) surface grid with 2‐m spacing in both horizontal directions, and four borehole arrays with 3.7‐m electrode spacing and 25.6‐m total depth. The primary contaminants, tetrachloroethylene (PCE) and trichloroethylene (TCE), are known to undergo redox reactions in the environment. Variations in the subsurface redox conditions are proposed as an electrochemical source for the SP signals measured in this investigation. A 3‐D self‐potential inversion algorithm is used to find an electrical current source model, taking into account the resistivity structure derived from a 3‐D spectral induced polarization survey at the same field location. The sources and sinks of electrical current can be related to the zones of relative high or low redox potential and are therefore interpreted in the context of contaminated areas. These results are reasonably correlated with DNAPL concentration data obtained from several ground‐truth well measurements, indicating that the SP sources can be an indicator of contaminated areas where electrochemical source mechanisms are active. In several cases, however, the SP sources and contaminant concentrations are not correlated, reflecting the spatial variability of biogeochemical parameters in the Earth that control the SP response in addition to concentration. More extensive geochemical ground‐truth information is therefore needed to validate the self‐potential source inversion methodology and develop it as a predictive tool in the context of contaminated sites.

Factors Affecting Effectiveness and Efficiency of DNAPL Destruction Using Potassium Permanganate and Catalyzed Hydrogen Peroxide

This paper describes laboratory studies conducted to evaluate the impact of varying environmental conditions (dense nonaqueous phase liquid (DNAPL) type and mass, and properties of the subsurface porous media) and design features (oxidant type and load) on the effectiveness and efficiency of in situ chemical oxidation (ISCO) for destruction of DNAPL contaminants. Porous media in 160 mL zero-headspace reactors were employed to examine the destruction of trichloroethylene and perchloroethylene by the oxidants potassium permanganate and catalyzed hydrogen peroxide. Measures of oxidation effectiveness and efficiency include (1) media demand (mg-oxidant/kg-porous media), (2) oxidant demand (mol-oxidant/mol-DNAPL), (3) reaction rate constants for oxidant and DNAPL depletion ( min−1 ) , (4) the percent (%) DNAPL destroyed, and (5) the relative treatment efficiency, i.e., the rate of oxidant depletion versus rate of DNAPL destruction. While an obvious goal of ISCO for DNAPL treatment is high effectiveness (i.e., ...