DNAPL Research Articles

Ebullition-facilitated mobilization of trapped dense non-aqueous phase liquid at residual saturation from sandy sediments.

Gas ebullition can mobilize dense non-aqueous phase liquids (DNAPLs) from sediments to the overlying water column, increasing the DNAPL-impacted area and posing serious challenges to the remediation and management of contaminated sediments. Despite this, there have been few laboratory studies focused on gas ebullition-facilitated transport of DNAPL. In this study, bubble-facilitated transport was investigated by injecting gas (air or nitrogen) at 1mL/min through a creosote source zone (∼25% saturation) capped with sand layers of different thicknesses. Three short-term experiments (8.3-8.7h) were capped with 11.4, 7.0 or 4.5cm of sand to estimate DNAPL flux. One long-term experiment (30 days) was capped with 8cm of sand to investigate DNAPL removal. Heptane placed on a layer of water above the sand was used as a solvent trap and analyzed for petroleum hydrocarbons (PHCs). Results showed that creosote travelled as thin coatings and films surrounding gas bubbles migrating out of the source zone. Gas invasion was dominated by capillarity in the 11.4cm-thick sand layer and by fracturing in the 7.0 and 4.5cm-thick sand layers. Migration through these fractures often led to the formation of creosote tails on mobilized bubbles that drained towards the rear end of the bubble. The mass released decreased exponentially with sand cap thickness. In the long-term experiment, images showed significant depletion of the source zone in 30 days. Linear regression analysis showed that relationships with high predictive capabilities for ebullition-facilitated fluxes of hydrophobic organic contaminants can be obtained by incorporating gas ebullition flux and source strength, based on results from this study along with others from the field and laboratory. To our knowledge, this is the first study to compile and integrate data collected from laboratory and field studies to develop an assessment tool to facilitate the management of contaminated sediments affected by gas ebullition.

Identification of chlorohydrocarbon degradation pathways in aquitards using dual element compound-specific isotope measurements in aquifers

Compound-specific isotope analysis (CSIA) has been increasingly used to understand and quantify the (bio)degradation processes affecting chlorohydrocarbons in aquifer-aquitard systems. In this study, we aimed at investigating through reactive transport simulations if dual element (C, Cl) CSIA in aquifer samples can provide information about the occurring (bio)degradation pathways in the underlying aquitard. To that end, we modeled the continous dissolution of a 1,1,2,2-tetrachloroethane (TeCA) dense nonaqueous phase liquid (DNAPL) source in an aquifer as well as the resulting TeCA groundwater plume formation and diffusion into the underlying aquitard. The (bio)degradation of TeCA in the aquifer-aquitard system was simulated in four scenarios: TeCA biodegradation via dehydrohalogenation to trichloroethene (TCE) and TeCA dichloroelimination to dichloroethene (DCE) in the aquifer as well as in the aquitard. The simulations revealed that dual element (C, Cl) CSIA in the aquifer allows the disentanglement of whether TeCA degradation occurs in the aquifer or the aquitard and which (bio)degradation pathways occur in the aquitard. This demonstrates that chlorohydrocarbon (bio)degradation pathways in aquitards can be identified based on CSIA aquifer measurements only, which is an advantage as aquifers are easier to monitor than aquitards.

Peroxide stabilizers remarkably increase the longevity of thermally activated peroxydisulfate for enhanced ISCO remediation

Thermally activated peroxydisulfate In Situ Chemical Oxidation (TAP-ISCO) is often applied for the remediation of soil-sorbed hydrophobic organic contaminants (HOCs) and nonaqueous phase liquids (NAPLs), which act as long-term sources of groundwater contamination. TAP-ISCO benefits from improved desorption/dissolution of organic contaminants into the aqueous phase and efficient activation of peroxydisulfate at elevated temperatures, but the primary limitation of TAP-ISCO is the short lifetime of peroxydisulfate (therefore the availability of reactive radical species). To resolve this problem, coupling of peroxide stabilizers with TAP were tested. The compatibility of seven representative commercial organic and inorganic peroxide stabilizers, including sodium stannate, trisodium phosphate, sodium pyrophosphate, sodium silicate, sodium citrate, ethylene diamine tetra methylene phosphonic acid and ethylenediaminetetraacetic acid disodium salt, with TAP in aqueous solutions and solutions containing goethite or soil particles were first studied. The effects of stabilizers on the formation, distribution and reactivity of reactive oxygen species were then investigated through electron paramagnetic resonance (EPR) spin-trapping experiments using 5,5-dimethyl-1-pyrroline-N-oxide, chemical probe experiments using anisole, nitrobenzene and hexachloroethane, and biphasic trichloroethylene (TCE) dense nonaqueous phase liquids (DNAPLs) TAP-ISCO mimicking experiments. The results indicate that organic stabilizers significantly accelerate peroxydisulfate decomposition at both ambient and elevated temperatures. In contrast, inorganic stabilizers can markedly increase peroxydisulfate longevity by suppressing the acid-catalyzed peroxydisulfate decomposition, quenching radical-chain acceleration, and sequestering transition metal species. In addition, TAP systems containing inorganic stabilizers can effectively generate a variety of reactive radical species, including SO4•−, HO•, and O2•−, and improve the oxidation of anisole and nitrobenzene, though suppressing the reduction of hexachloroethane to some extent. Especially, suitable inorganic stabilizers (e.g., trisodium phosphate) can effectively improve TAP oxidation of TCE DNAPL while suppressing peroxydisulfate decomposition. Overall, this study provides the fundamental basis of coupling TAP-ISCO with peroxide stabilizers.

A new analytical model for transport of multiple contaminants considering remediation of both NAPL source and downgradient contaminant plume in groundwater

The contamination of groundwater aquifers by chlorinated solvents is a water-resource issue of great importance worldwide. Such contaminants are difficult to treat because they are often released as dense non-aqueous phase liquids (DNAPLs). Research shows that the application of remediation technologies to both the NAPL source and dissolved plume can lead to more efficient remediation, rather than to either alone. In these remediation efforts, analytical models that evaluate behavior and fate of contaminants do provide a better understanding of the performance of these remedial technologies. To the best of our knowledge, there exist no analytical model of simulating the plume migration of multiple contaminants with capabilities of accounting for both NAPL source and plume remediation simultaneously and different retardation for original chlorinated solvent contaminant and its degradation byproducts. In this study, we present a new analytical model for remediating both NAPL source and downgradient contaminant plume in groundwater at sites contaminated with chlorinated solvents and their degradation products with different retardation factors as well as considering both NAPL source and plume remediation simultaneously. A source model that accounts for the depletion of mass by the processes of dissolution or first-order decay reactions, corresponding with the removal or destruction of the source mass, is coupled to a plume reactive transport model. The source model is accounted for by relating source mass to the flux-averaged source discharge concentration through a power function. The developed analytical model considers 1-D advection, 3-D dispersion, first-order decay reactions and ingrowth as well as linear isothermal equilibrium sorption. The proposed analytical solution was derived through successive application of the Laplace transform in time and the double finite Fourier cosine transform regarding y and z. The correctness of the analytical model and its auxiliary FORTRAN computer program code are proved by showing excellent agreements between the simulated plume concentrations of all contaminants obtained from the derived analytical model and from a semi-analytical model available in the literature. Application of the proposed analytical solutions illustrates that the use of identical retardation factors for all contaminants may lead to underestimation or overestimation of the mobility of the contaminants, in cases when the retardation factors of the individual contaminants are greatly different from the identical retardation factor value adopted in all contaminants. From the experiments on six scenarios corresponding six remedial treatments, we found out that both the enhanced source decay and partial removal of source mass are main controlling factors at reducing the concentrations of all the contaminants, whereas plume decay leads to effective reduction in the concentrations of PCE, however, rather it causes unfavorable increases of the concentrations of the degradation byproducts.Ultimately, the developed model is used to better understand the impacts of various possible combinations of remedial efforts and management decisions on remediation of the subsurface contamination and quantify the benefit of a certain remediation decision.

Pore-Scale Mechanisms of Solid Phase Emergence During DNAPL Remediation by Chemical Oxidation.

In situ chemical oxidation (ISCO) has proven successful in the remediation of aquifers contaminated with dense nonaqueous phase liquids (DNAPLs). However, the treatment efficiency can often be hampered by the formation of solids or gas, reducing the contact between remediation agents and residual DNAPLs. To further improve the efficiency of ISCO, fundamental knowledge is needed about the complex multiphase flow and reactive transport processes as new solid and fluid phases emerge at the microscale. Here, via microfluidic experiments, we study the pore-scale dynamics of trichloroethylene degradation by permanganate. We visualize how the remediation evolves under the influence of solid phase emergence and explore the roles of injection rate, oxidant concentration, and stabilization supplement. Combining image processing, pressure analysis, and stoichiometry calculations, we provide comprehensive descriptions of the oxidant concentration-dependent growth patterns of the solid phase and their impact on the remediation efficiency. We further corroborate the stabilization mechanism provided by phosphate supplement, which is effective in inhibiting solid phase generation and thus highly beneficial for the oxidation remediation. This work elucidates the pore-scale mechanisms during remediation of chlorinated solvents with a particular context in the solid phase production and the associated effects, which is of general significance to understanding various processes in natural and engineered systems involving solid phase emergence or aggregation phenomena, such as groundwater and soil remediation.

Forward and back diffusion of reactive contaminants through multi-layer low permeability sediments

Contaminants stored in the low permeability sediments will continue to threaten the adjacent shallow groundwater system after the aquifer is remediated. Understanding the storage and discharge behavior of contaminants in the aquitards is essential for the efficient remediation of contaminated sites, but most of the previous analytical studies focused on nonreactive solutes in a single homogenous aquitard. This study presents novel analytical solutions for the forward and back diffusion of contaminants through multi-layer low permeability sediments considering abiotic and biotic environmental degradation. Three representative source depletion patterns (i.e., instantaneous, linear, and exponential patterns) were selected to describe the dissolution of dense non-aqueous phase liquids (DNAPL) in the aquifer more realistically. At the forward diffusion stage, the mass storage of contaminants in the aquitards with the instantaneous pattern is the largest, nearly twice that with the exponential pattern. A simple equivalent homogeneous model is generally adopted in the risk assessment. However, relative to the proposed multi-layer model, it will significantly underestimate the onset of the back-diffusion of heterogeneous aquitards and overestimate the persistence of aquifer plumes. The previously-reported semi-infinite boundary assumption is also not applicable, with a maximum error of over 200% in the long-term prediction of back diffusion behavior of a thin aquitard. Moreover, when the degradation half-life is less than 16 years, less than 10% of the contaminants stored in the aquitards will diffuse into the overlying aquifer, suggesting that biostimulation or bioaugmentation can effectively mitigate back-diffusion risk. Overall, the proposed diffusion-reaction coupled model with multi-layer media is of great value and high demand in predicting the back-diffusion behavior of heterogeneous aquitards and guiding the soil bioremediation.

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.

Enhanced semi-volatile DNAPL accessibility at sub-boiling temperature during electrical resistance heating in heterogeneous porous media

Successful remediation of semi-volatile contaminants using electrical resistance heating (ERH) coupled technologies requires a deep understanding of contaminant migration and accessibility, especially with stratigraphic heterogeneity and dense nonaqueous phase liquid (DNAPL) occurrence. Here, we chose nitrobenzene (NB) as a model contaminant of semi-volatile DNAPL and uniquely demonstrated that temperature variation during ERH could induce NB DNAPL migration out of the low permeability zone (LPZ) even below water boiling temperature. When heating the system using alternating current (AC) of 140 V to a temperature range of 50–79 °C, obvious DNAPL migration was visually observed. The upward migration of DNAPL would considerably increase the mass of accessible contaminant by other remediation measures. The downstream cumulative NB mass of 1092 mg in 140 V system raised 56-folds compared to that of 19 mg in the control experiment with only groundwater flow. This migration was mainly attributed to a complex natural convection caused by temperature gradient. Comparing with traditional AC heating, ERH powered by pulsed direct current (PDC-ERH) showed a higher and more uneven heating pattern, resulting in a stronger convection at the same voltage that enhanced the DNAPL migration out of LPZ. These results revealed the importance of natural convection in the ERH process, which could be further optimized to improve the energy efficiency of remediation.

A novel hydrocyclone for use in underground DNAPL phase separation

Halogenated organic solvents are the most commonly detected pollutants in groundwater and are particularly toxic and harmful. How to separate these dense nonaqueous phase liquid (DNAPL) pollutants efficiently from groundwater has become an important research question. Here, a novel hydrocyclone with annular overflow structure was designed, which eliminated the short-circuit flow of the traditional hydrocyclone and solved the problem of overflow entrainment caused by the enrichment of droplets near the locus of zero vertical velocities (LZVV) into turbulence. The flow field characteristics of this novel hydrocyclone were studied using Computational Fluid Dynamics (CFD) simulation and compared with the traditional hydrocyclone. It was found that the annular gap structure of the novel hydrocyclone increased the tangential velocity of the outer vortex. Moreover, the radius of the LZVV was expanded outward by 0.17 mm, which reduced the possibility of droplets with small particle sizes in the second phase escaping from the overflow pipe. The collective effect was to eliminate the short-circuit flow. This novel hydrocyclone was able to separate DNAPL pollutants with low consumption and high efficiency, across a range of inlet velocity from 4 to 6 m/s. The maximum separation efficiency was 99.91 %. In addition, with trichloroethylene (TCE) as the target pollutant, the maximum volume fraction of the dispersed phase in the hydrocyclone was located on the side wall of the hydrocyclone. Taken together, we believe that this work will provide a low-cost, efficient separation method for the separation of groundwater- contaminated liquid mixtures. Furthermore, it has broad application prospects in the field of heterotopic remediation of groundwater.

Investigating the roles of advection and degradation in chlorinated solvent back-diffusion from multi-layer aquitards: A novel analytical approach

Aquitards contaminated by chlorinated solvents may act as a secondary source slowly releasing contaminants into adjacent aquifers, thus severely hampering the remediation of groundwater systems. Accurate predicting the long-term exchange of solvents between aquifers and aquitards can more effectively guide site management and remediation. This study presented a general analytical model for the back-diffusion of chlorinated solvents through multilayer aquitards. This model considers the slow advection and local degradation of dissolved constituents in natural aquitards and the dynamic depletion of dense nonaqueous phase liquid (DNAPL) source zone in aquifers. Transient solutions for the proposed multilayer model were derived using Duhamel’s Theorem, the separation of variables method, and the transfer matrix method, verified against experimental and numerical concentration data. Results reveal that advection in aquitards can significantly shorten the trailing time of chlorinated solvent plumes, and highly adsorptive soils may reduce this effect in layered aquitards. The previous no-degradation model is no longer applicable to predict the back-diffusion behavior of chlorinated solvents when the extent and rate of solvent degradation are large, giving a “strong-effect zone”. Based on numerous example simulations and data fitting, the forecast functions for the back-diffusion onset time and plume trailing time were proposed, greatly facilitating remediation decisions and risk assessment of chlorinated-solvent contaminated sites.

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.

Investigating the migration of immiscible contaminant fluid flow in homogeneous and heterogeneous aquifers with high-precision numerical simulations.

Numerical modeling of the migration of three-phase immiscible fluid flow in variably saturated zones is challenging due to the different behavior of the system between unsaturated and saturated zones. This behavior results in the use of different numerical methods for the numerical simulation of the fluid flow depending on whether it is in the unsaturated or saturated zones. This paper shows that using a high-resolution shock-capturing conservative method to resolve the nonlinear governing coupled partial differential equations of a three-phase immiscible fluid flow allows the numerical simulation of the system through both zones providing a unitary vision (and resolution) of the migration of an immiscible contaminant problem within a porous medium. In particular, using different initial scenarios (including impermeable “lenses” in heterogeneous aquifers), three-dimensional numerical simulation results are presented on the temporal evolution of the contaminant migration following the saturation profiles of the three-phases fluids flow in variably saturated zones. It is considered either light nonaqueous phase liquid with a density less than the water, or dense nonaqueous phase liquid, which has densities greater than the water initially released in unsaturated dry soil. Our study shows that the fate of the migration of immiscible contaminants in variably saturated zones can be accurately described, using a unique mathematical conservative model, with different evolution depending on the value of the system’s physical parameters, including the contaminant density, and accurately tracking the evolution of the sharp (shock) contaminant front.

Effects of co-occurrence of PFASs and chlorinated aliphatic hydrocarbons on microbial communities in groundwater: A field study

The effects of per- and polyfluoroalkyl substances (PFASs) and chlorinated aliphatic hydrocarbons (CAHs) co-contamination on the microbial community in the field have not been studied. In this study, we evaluated the presence of PFASs and CAHs in groundwater collected from a fluorochemical plant (FCP), and carried out Illumina MiSeq sequencing to understand the impact of mixed PFASs and CAHs on the indigenous microbial community. The sum concentrations of 20 PFASs in FCP groundwater ranged from 2.05 to 317.40 μg/L, and the highest PFOA concentration was observed in the deep aquifer (60 m below ground surface), co-contaminated by dense non-aqueous-phase liquid (DNAPL). The existence of PFASs and CAHs co-contamination in groundwater resulted in a considerable decrease in the diversity of microbial communities, while the abundance of metabolisms associated with contaminants biodegradation has increased significantly compared to the background wells. Furthermore, Acinetobacter, Pseudomonas and Arthrobacter were the dominant genera in PFASs and CAHs co-contaminated groundwater. The presence of high concentrations of PFASs and CAHs has been positively associated with the genus of Citreitalea. Finally, geochemical parameters, such as ORP, sulfate and nitrate were the key factors to shape up the structure of the microbial community and sources to rich the abundance of the potential functional bacteria.

Anaerobic degradation of benzene and other aromatic hydrocarbons in a tar-derived plume: Nitrate versus iron reducing conditions

The anaerobic degradation of aromatic hydrocarbons in a plume originating from a Pintsch gas tar-DNAPL zone was investigated using molecular, isotopic- and microbial analyses. Benzene concentrations diminished at the relatively small meter scale dimensions of the nitrate reducing plume fringe. The ratio of benzene to toluene, ethylbenzene, xylenes and naphthalene (BTEXN) in the fringe zone compared to the plume zone, indicated relatively more loss of benzene in the fringe zone than TEXN. This was substantiated by changes in relative concentrations of BTEXN, and multi-element compound specific isotope analysis for δ2H and δ13C. This was supported by the presence of (abcA) genes, indicating the presumed benzene carboxylase enzyme in the nitrate-reducing plume fringe. Biodegradation of most hydrocarbon contaminants at iron reducing conditions in the plume core, appears to be quantitatively of greater significance due to the large volume of the plume core, rather than relatively faster biodegradation under nitrate reducing conditions at the smaller volume of the plume fringe. Contaminant concentration reductions by biodegradation processes were shown to vary distinctively between the source, plume (both iron-reducing) and fringe (nitrate-reducing) zones of the plume. High anaerobic microbial activity was detected in the plume zone as well as in the dense non aqueous phase liquid (DNAPL) containing source zone. Biodegradation of most, if not all, other water-soluble Pintsch gas tar aromatic hydrocarbon contaminants occur at the relatively large dimensions of the anoxic plume core. The highest diversity and concentrations of metabolites were detected in the iron-reducing plume core, where the sum of parent compounds of aromatic hydrocarbons was greater than 10 mg/L. The relatively high concentrations of metabolites suggest a hot spot for anaerobic degradation in the core of the plume downgradient but relatively close to the DNAPL containing source zone.

DNAPL flow and complex electrical resistivity evolution in saturated porous media: A coupled numerical simulation

Induced Polarization (IP) is a non-intrusive geophysical method to monitor Dense Non-Aqueous Phase Liquid (DNAPL) contamination and remediation processes underground. In this study, an advanced numerical code simulating DNAPL flow and complex electrical resistivity is presented. The model was validated against existing IP results and image measurements that were carried out previously in a series of 2D tank experiment. Multiphase flow modeling in porous media is coupled with electrical current modeling to simulate the process of DNAPL migration and the associated IP response. This brings a broader view of the contamination in space and time compared to surface and borehole measurements, especially when the results are supported by field measurements or laboratory experiments. The simulations are developed in 3D and are performed in COMSOL Multiphysics®. The simulations using petrophysical relationships for in-phase and quadrature resistivity and the results of the experiments are in complete accordance with each other in the parts of the tank where the saturation of DNAPL is relatively low (i.e. especially in the cone of depression in the pumping scenario). However, the parts associated with high saturation of DNAPL show high errors between the in-phase resistivity simulations and the results from experiments. The present work can be regarded as a preliminary study toward further applications of coupled IP-multiphase flow for more accurate detection and monitoring of DNAPLs. It is suggested that the choice of tool/approach in this study be extended to larger-scale studies for further investigation.

Density-modification displacement using colloidal biliquid aphron for entrapped DNAPL contaminated aquifer remediation

Colloidal biliquid aphron (CBLA) is a strong density modifier for dense nonaqueous phase liquids (DNAPLs). However, the underlying mechanisms responsible for density modification and displacement is not yet clear. Here, a series of batch column and sandbox experiments were conducted to achieve substantial removal and irreversible density reduction of tetrachloroethylene (PCE). The mass of PCE retained in the column and sandbox was less than 1% under suitable injection conditions, and the density of PCE in the effluent was less than that of water (fluctuated in the range of 0.74–0.96 g/cm3). The displacement process was controlled by the high viscosity ratio of CBLA to PCE (52.3). The emulsified and dissolved phase of PCE formed after reaction with CBLA, and the light nonaqueous phase liquid (LNAPL) phase formed after injecting demulsifier solution. The phase analysis played a significant role in monitoring the changes in concentration and density of PCE. The density-modification displacement technique using CBLA reduced the mass of residual PCE by a factor of 165 compared to surfactant flushing, and there was no risk of downward migration of PCE. This study contributes to a better remediation of entrapped DNAPL in contaminated aquifer.

Deep learning based optimization under uncertainty for surfactant-enhanced DNAPL remediation in highly heterogeneous aquifers

The optimization for surfactant-enhanced aquifer remediation (SEAR) of dense non-aqueous phase liquid (DNAPL)-contaminated aquifers is usually accompanied by uncertainties, which may arise from the characterization of complex aquifer heterogeneity and DNAPL source zone architecture (SZA) due to measurement sparsity. Optimization under uncertainty is computationally expensive as it involves an enormous number of model runs. The huge computational burden can be alleviated by utilizing a surrogate model for repeated model evaluations. However, most of the developed surrogates are often limited to low-dimensional optimization problems that only consider simplified aquifer heterogeneity. In this study, we developed a multi-objective simulation-optimization framework to optimize the SEAR schemes considering the characterization uncertainties from both highly heterogeneous aquifer permeability and complex SZA. A fast-to-run convolutional neural network (CNN)-based surrogate model was developed to approximate the high-dimensional and highly complex input-output mapping of the DNAPL multiphase flow simulation model. We first used the rejection sampling strategy to generate random realizations of permeability and SZA conditioning on their limited measurements and then formulated a multi-objective optimization under uncertainty problem based on these realizations. The developed 3-D CNN was trained and used as the surrogate for repeated model runs in optimization to identify the optimal SEAR schemes under uncertainty. A 3-D numerical experiment was used to test the performance of the CNN-based simulation-optimization framework. Comprehensive analysis on the obtained Pareto fronts demonstrates that the proposed framework can efficiently identify reliable Pareto-optimal solutions with a 99.8% speedup compared to the traditional optimization coupled with the forward model. Moreover, the optimization considering multiple realizations enables us to perform the risk assessment to locate the risk zone where the NAPL phase possibly exists after remediation, which provides useful information for decision-making.

Evaluating the Hydraulic Conductivity of Dense Nonaqueous Phase Liquid in a Single Fracture of Rock-like Material

To investigate the seepage characteristics of dense nonaqueous phase liquids (DNAPLs) in rock fractures, two types of NAPLs (paint and creosote) were used in triaxial permeability tests conducted on single-fracture samples. The hydraulic conductivity of rock fractures with different apertures, confining pressures, and fluid properties was measured, and the influence of various physical factors on transmissivity was explored. The results demonstrated the following: (1) Fracture aperture and fluid viscosity are the main factors influencing transmissivity; (2) The widely used cubic law fails to effectively predict the transmissivity of high-viscosity liquids in a fracture, and the influence of liquid viscosity is considerably higher than that predicted by the cubic law; and (3) This study proposed a transmissivity prediction model of DNAPLs in a rock fracture based on multivariate regression analysis. The proposed model provides more accurate prediction results than those predicted by the cubic law, and is applicable to fracture apertures ranging from 5 × 10−4 to 2.5 × 10−3 m as well as to every kind of fluid used in this study.

Enhanced-solubilization and dissolution of multicomponent DNAPL from homogeneous porous media

The presence of multicomponent dense nonaqueous phase liquid (DNAPL) mixtures in porous media can significantly limit the effectiveness of groundwater remediation. A series of column transport and flushing experiments were conducted to quantify the impact of various enhanced flushing agents on dissolution and removal of a multicomponent DNAPL source within a macroscopically homogeneous porous medium. The columns were established with NAPL saturations consisting of an equal mole mixture of cis-1,2-dichloroethene, trichloroethene, and tetrachloroethene. The solubilization agents used included two complexing sugars - hydroxypropyl-β-cyclodextrin (HPCD and methyl-β-cyclodextrin (MCD); a surfactant - sodium dodecyl sulfate (SDS); and a cosolvent - ethanol (EtOH). The chemical flushing agents greatly reduced the time needed to remove each DNAPL component, compared to flushing with water alone. Initial DNAPL-component elution concentrations were successfully predicted using Raoult's Law for MCD, HPCD, and water flushing, indicating that ideal dissolution was initiated by the lower-power enhanced-solubilization agents. EtOH was most efficient at removing the contaminants in terms of normalized mass recovery but least efficient based on a mass-ratio and mole-ratio of contaminant to reagent analysis. SDS was most efficient for contaminant removal when analyzed based on mass-contaminant to mass-reagent recovered and MCD was most effective based on a moles-contaminant to moles-reagent recovered efficiency evaluation. However, in terms of mass flux reduction analysis (i.e. removal metric), SDS was least efficient for contaminant removal compared to all other enhanced-flushing agents tested, especially during the initial stages of DNAPL removal. Results from this study indicate that ideal dissolution was initiated during enhanced-solubilization and that several criteria should be used to evaluate the removal effectiveness of flushing agents for multi-component NAPL systems.