DNAPL Research Articles

Optimized survey design for the joint use of direct current resistivity and induced polarization: Monitoring of DNAPL source zone evolution at a virtual field site.

The combined application of direct current (DC) resistivity and induced polarization (IP) methods, referred to as combined DCIP method, has gained popularity for characterizing the critical zone dynamic processes such as dense non-aqueous phase liquids (DNAPLs) spreading at contaminated sites. Large-scale DCIP surveys typically require considerable durations, necessitating optimized survey designs to enhance survey resolution while controlling time and labor costs. However, to date, approaches to optimize geoelectrical survey design have focused solely on DC applications, and the efficiency of optimized survey designs for combined DCIP is yet to be investigated. Moreover, as subsurface heterogeneity would impact the geophysical observations, most field-scale numerical DCIP studies have still been conducted at artificial sites that lacked realistic aquifer heterogeneity, which could affect the validity of the DCIP survey evaluations. In this work, a virtual geoenvironmental field site based on high-resolution real aquifer analog was created to simulate a DNAPL evolution scenario with simultaneous monitoring by DCIP survey, employing both the optimized survey design and popular non-optimized survey designs (Wenner, Wenner-Schlumberger, Dipole-Dipole arrays). Results show that the optimized survey with prior information improves the monitoring accuracy of DNAPL source zone (SZ) by 8 to 19% with respect to different DCIP characteristics (conductivity, chargeability, normalized chargeability, and relaxation time). Another ideal numerical test indicates that the optimized survey shows up to an 83% reduction in measurement time compared to the conventional survey, while maintaining the same subsurface image resolution. Additionally, the optimized surveys designed without or with limited prior information were also shown to be more efficient than conventional survey for imaging the entire subsurface space. The findings in this study highlight the immense potential of optimized survey design methods for enhancing the efficiency of DCIP surveys on subsurface contaminants and hydrological processes.

Research Hotspots and Trend Analysis in Modeling Groundwater Dense Nonaqueous Phase Liquid Contamination Based on Bibliometrics

Groundwater contamination by dense nonaqueous phase liquids (DNAPLs) poses a severe environmental threat due to their persistence and toxicity. Modeling DNAPL contamination is essential for understanding their distribution, predicting contaminant spread, and developing effective remediation strategies, but it is also challenging due to their complex multiphase behavior. Over the past few decades, researchers have developed various models, including multiphase flow, mass transfer, and solute transport models, to simulate the distribution of DNAPLs. To understand the research trends in DNAPL modeling in groundwater, a bibliometric analysis was conducted using CiteSpace based on 614 publications from the WoS Core Collection database (1993–2023). The publications were statistically analyzed, and the research hotspots and trends were summarized. The statistical analysis of the publications indicates that the United States is leading the international research on DNAPL models, followed by China and Canada; the collaboration between countries and disciplines in this field needs to be strengthened. Keyword clustering and burst detection reveal that the current research hotspots focus on multiphase flow models, mass transfer models, back diffusion, and practical applications of the models; the research trends are centered on back diffusion mechanisms, the characterization of contamination source zones, and prediction of the contaminant distribution at real-world sites, as well as optimization of the remediation strategies.

Impact of Magnetic Fields on the Efficiency of Dense Non-Aqueous Phase Liquid Removal from Unsaturated Zones Using Steam Injection

Unsaturated zone is of great importance in providing water and nutrients that are vital to the biosphere and the main factor controlling water movement from the land surface to the aquifer. Contamination of unsaturated zone by Dense Non-Aqueous Phase Liquids (NAPLs) has becoming major threat to human environment as a result of increasing concern with industrialization. The use of steam injection for remediation of porous media which are contaminated by DNAPLs has not given the desire recovery efficiency, hence the need for improvement in recovery efficiency has been a subject of continuous study. This study investigated the effect of magnetic field on the removal of DNAPL from unsaturated zone using steam injection. An unsaturated zone of a sand box of interior dimensions 110 x 74 x 8.5 cm was polluted at different periods with 200 ml of Carbon tetrachloride. Steam injection experiment with flow rate of 0.01 m3/s was performed to determine the recovery efficiencies of Carbon tetrachloride in an unsaturated zone containing sand of porosity 0.42 and permeability of 0.001163779 cm/s. Magnetic field in step of 1 Tesla (T) was introduced from 1-3 Tesla (T) into experiment. The effects of magnetic field on removal of DNAPL from unsaturated zone using steam injection only and steam injection with magnetic field were compared using descriptive statistic. The recovery efficiency of Carbon tetrachloride using steam injection only was 82.05 %, while that with varying magnetic field at 1T, 2T and 3T were 89.45%, 94.95% and 95.35% respectively. The recovery efficiency of steam injection with varying magnetic field at 1T, 2T and 3T were 9.02, 15.72, 16.21% higher than the result of steam injection only for Carbon tetrachloride. The result demonstrated the ability of steam injection to recover contaminants from the subsurface. The application of magnetic field as an aid to facilitate system activities has been signifi-cantly effective due to its ability to overcome the constraints of conventional treatment processes. A combined application of steam injection with magnetic field appreciably enhances the removal of Non Aqueous phase liquids from Unsaturated Zone.

Density modification of DNAPL using self-demulsifying colloidal biliquid aphron: Kinetics, mechanisms and influencing factors

Density-modification remediation of dense nonaqueous phase liquid (DNAPL) using colloidal biliquid aphron (CBLA) is an efficient means of enhancing flushing and avoiding the risk of downward migration of DNAPL. However, the use of demulsifier is currently necessary for CBLA to achieve density modification. This leads to issues such as low modification efficiency and the risk of secondary contamination. In this work, we developed a self-demulsifying CBLA (PO-CBLA-S) for density-modification remediation of DNAPL, eliminating the need for external demulsifiers. The self-demulsification process exhibited pseudo-secondary reaction kinetics, achieving densities below 1 g/cm3 for various DNAPLs. Groundwater chemistry parameters (pH, anions, cations, temperature, and humic acid (HA) content) were investigated for their impact on perchloroethylene (PCE) density modification. Cations were found to enhance PO-CBLA-S density modification more than anions. Both strong acidic and alkaline environments promote the density regulation of PCE by PO-CBLA-S, and temperature positively correlates with the efficiency of density modification. High concentrations of HA also have a favorable facilitating effect on the density modification. The mechanisms of self-demulsifying density modification were clarified at the microscale. Surfactant entanglement caused by internal surfactant-solvent interaction decreased the stability of PO-CBLA-S, leading to self-demulsification. This study addresses density modification challenges and provides a theoretical foundation for its groundwater remediation applications.

Mapping and monitoring dense non-aqueous phase liquid source zone by fused surface and cross-borehole electrical resistivity tomography

Effective characterization of dense non-aqueous phase liquid (DNAPL) source zones is crucial for remediating polluted sites. DNAPL often reside as residuals or pools within high-permeability lenses and above impermeable layers due to soil heterogeneity, gravity, and capillary barriers. Given the high cost of drilling, electrical resistivity tomography (ERT) techniques—including surface ERT and cross-borehole ERT, are commonly used for DNAPL source zone mapping and monitoring. However, the low spatial resolution of ERT increases uncertainty in source zone investigations. This study proposes a method for improving DNAPL mapping and monitoring by fusing surface and cross-borehole ERT data. Sandbox experiments were conducted to simulate a heterogeneous DNAPL source zone, employing both ERT methods for static mapping and dynamic monitoring. Reflective light imaging (RLM) was used to visualize DNAPL migration and provide saturation data, allowing for the quantification of ERT's effectiveness in characterizing DNAPL distribution. The results indicate that individual ERT methods face significant challenges in DNAPL source zone mapping due to background interference. Surface ERT alone tends to underestimate the extent of deeper DNAPL source zones. However, fusing surface and cross-borehole ERT results in a complementary enhancement of vertical spatial resolution, thereby improving the characterization of DNAPL source zones. The fusion of static and time-lapse ERT data substantially enhances DNAPL source zone mapping and monitoring capabilities. By calculating the ratio of the ERT-monitored area to the actual area using resistivity change contours (5 %, 10 %, 15 %), it was found that fusing surface and cross-borehole ERT data improved monitoring resolution by 50.48 % compared to surface ERT alone and by 22.95 % compared to cross-borehole ERT. Principal component analysis (PCA) was effective in fusing time-lapse data, while the weighted average method (WAM) outperformed PCA for static resistivity data fusion.

Quantifying remediation of chlorinated volatile compounds by sulfidated nano zerovalent iron treatment using numerical modeling and CSIA

Sulfidated nanoscale zerovalent iron (S-nZVI) has demonstrated promising reactivity and longevity for remediating chlorinated volatile compounds (cVOC) contaminants in laboratory tests. However, its effectiveness in field applications remains inadequately evaluated. This study provides the first quantitative evaluation of the long-term effectiveness of carboxymethyl cellulose-stabilized S-nZVI (CMC-S-nZVI) at a cVOC-contaminated field site. A reactive transport model-based numerical approach delineates the change in cVOC concentrations and carbon isotope values (i.e., δ13C from compound-specific stable isotope analysis (CSIA)) caused by dissolution of dense non-aqueous phase liquid, sorption, and pathway-specific degradation and production, respectively. This delineation reveals quantitative insights into remediation effectiveness typically difficult to obtain, including extent of degradation, contributions of different degradation pathways, and degradation rate coefficients. Significantly, even a year after CMC-S-nZVI application, degradation remains an important process effectively removing various cVOC contaminants (i.e., chlorinated ethenes, 1,2-dichloroethanes, and chlorinated methanes) at an extent varying from 5 %-62 %. Although the impacts of CMC-S-nZVI abundance on degradation vary for different cVOC and for different sampling locations at the site, for the primary site contaminants of tetrachloroethene and trichloroethene, their predominance of dichloroelimination pathway (≥ 88 %), high degradation rate coefficient (0.4–1.7 d-1), and occurrence at locations with relatively high CMC-S-nZVI abundance strongly indicate the effectiveness of abiotic remediation. These quantitative assessments support that CMC-S-nZVI supports sustainable ZVI-based remediation. Further, the novel numerical approach presented in this study provides a powerful tool for quantitative cVOC remediation assessments at complex field sites where multiple processes co-occur to control both concentration and CSIA data.

Examining site intervention efficacy and uncertainties with conceptual Bayesian networks: preventing offsite migration of DNAPL and contaminated groundwater.

For contaminated sites, conceptual site models (CSMs) guide the assessment and management of risks, including remediation strategies. Recent research has expanded diagrammatic CSMs with structural causal modeling to develop what are nominally called conceptual Bayesian networks (CBNs) for environmental risk assessment. These CBNs may also be useful for problems of controlling and preventing offsite contaminant migration, especially for sites containing dense nonaqueous phase liquids (DNAPLs). In particular, the CBNs provide greater clarity on the causal relationships between source term, onsite and offsite migration, and remediation effectiveness characterization for contaminated DNAPL sites compared to traditional CSMs. These ideas are demonstrated by the inclusion of modifying variables, causal pathway analysis, and interventions in CBNs. Additionally, several new extensions of the CBN concept are explored including the representation of measurement variables as lines of evidence and alignment with conventional pictorial CSMs for groundwater modeling. Taken as a whole, the CBNs provide a powerful and adaptable knowledge representation tool for remediating subsurface systems contaminated by DNAPL.

Coupling of radon and microbial analysis for dense non-aqueous-phase liquid tracing and health risk assessment in groundwater under seasonal variations

Dense non-aqueous-phase liquids (DNAPLs) represent one of the most hazardous contaminants of groundwater, posing health risks to humans. Radon is generally used to trace DNAPLs; however, external factors, such as rainfall or stream water, can influence its efficacy. To overcome these limitations, this study pioneered the integration of radon and microbial community structures to explore DNAPL tracing and natural attenuation in the context of seasonal variations for human health risk assessments. The results showed that a radon tracer can estimate DNAPL saturation in the source zone, especially during the dry season when radon deficiency predominates. However, samples exhibited mixing effects during the wet season because of local precipitation. Moreover, bioremediation and low health risks were observed in the plume boundary zone, indicating that microbial dechlorination was a predominant factor determining these risks. The abnormal patterns of radon observed during the wet season can be elucidated by examining microbiological communities. Consequently, a combined approach employing radon and microbial analysis is advocated for the boundary zone, albeit with a less intensive management strategy, compared with that for the source zone. This novel coupling method offers a theoretical and practical foundation for managing DNAPL-contaminated groundwater.

Sustainable lindane waste remediation: Surfactant-driven residual DNAPL extraction and oxidation in a real landfill (LIFE SURFING)

The LIFE SURFING Project was carried out at the Bailin Landfill in Sabiñánigo, Spain (2020-2022), applying Surfactant Enhanced Aquifer Remediation (SEAR) and In Situ Chemical Oxidation (S-ISCO) in a 60-meter test cell beneath the old landfill, to remediate a contaminated aquifer with dense non-aqueous phase liquid (DNAPL) from nearby lindane production. The project overcame traditional extraction limitations, successfully preventing groundwater pollution from reaching the river.In spring 2022, two SEAR interventions involved the injection of 9.3 m3 (SEAR-1) and 6 m3 (SEAR-2) of aqueous solutions containing 20 g/L of the non-ionic surfactant E-Mulse 3®, with bromide (around 150 mg/L) serving as a conservative tracer. 7.1 and 6.0 m3 were extracted in SEAR-1 and SEAR-2, respectively, recovered 60–70 % of the injected bromide and 30–40 % of the surfactant, confirming surfactant adsorption by the soil. Approximately 130 kg of DNAPL were removed, with over 90 % mobilized and 10 % solubilized. A surfactant-to-DNAPL recovery mass ratio of 2.6 was obtained, a successful value for a fractured aquifer. In September 2022, the S-ISCO phase entailed injecting 22 m3 of a solution containing persulfate (40 g/L), E-Mulse 3® (4 g/L), and NaOH (8.75 g/L) in pulses over 48 h, oxidizing around 20 kg of DNAPL and ensuring low toxicity levels after that.Preceding the SEAR and S-ISCO trials, 2020 and 2021 were dedicated to detailed groundwater flow characterizations, including hydrological and tracer studies. These preliminary investigations allowed the design of a barrier zone between 317 and 557 m from the test cell and the river, situated 900 m away. This zone, integrating alkali dosing, aeration, vapor extraction, and oxidant injection, effectively prevented the escape of fluids to the river. Neither surfactants nor contaminants were detected in river waters post-treatment. The absence of residual phase in test cell wells and reduction of chlorinated compound levels in groundwater were noticed till one year after S-ISCO.

Bidirectional machine learning-assisted sensitivity-based stochastic searching approach for groundwater DNAPL source characterization.

In this study, we designed a machine learning-based parallel global searching method using the Bayesian inversion framework for efficient identification of dense non-aqueous phase liquid (DNAPL) source characteristics and contaminant transport parameters in groundwater. Swarm intelligence organized hybrid-kernel extreme learning machine (SIO-HKELM) was proposed to approximate the forward and inverse input-output correlation with a high accuracy using the DNAPL transport numerical simulation model. An adaptive inverse-HKELM was established for preliminary estimation of the source characteristics and contaminant transport parameters to correct prior information and generate high-quality initial starting points of parallel searching. A local accurate forward-HKELM surrogate of the numerical model was embedded in the searching system for avoiding repetitive CPU-demanding likelihood evaluations. A sensitivity-based Metropolis criterion (MC), incorporating the dynamic particle swarm optimization (SD-PSO) algorithm, was developed for improving the search ergodicity and realizing precise inversion of all the unknown variables with drastic variations in sensitivity to the likelihood function. Results showed that the generalization capability and robustness of SIO-HKELM were superior to those of the traditional machine learning methods, including KELM and support vector regression (SVR), and it sufficiently approximated the forward and inverse input-output mapping of the numerical model with testing determination coefficients of 0.9944 and 0.6440, respectively. With high-quality prior information and initial starting points generated by the adaptive inverse-HKELM feed approach, the uncertainty in the inversion outputs was reduced, and the searching process rapidly converged to reasonable posterior distributions in around 60 iterations. Compared with the widely used multichain Markov chain Monte Carlo (MCMC) approach, the parallel searching lines generated by SD-PSO-MC adequately covered the searching space, and the "equifinality" effect was more effectively restrained by reducing the relative errors of all the point estimations to less than 8%. Therefore, the real source information reflected by the statistical characteristics of the SD-PSO-MC inversion outputs was more precise than that obtained using the multichain MCMC approach.

Sustainable application of surfactants in soil remediation: Selective pollutants adsorption and hydrogen peroxide-driven adsorbent regeneration

The uncontrolled disposal of the liquid lindane wastes have led to the formation of dense non-aqueous phase liquids (DNAPL), consisting of 28 chlorinated organic compounds (COCs), contaminating soil and groundwater. Surfactant-enhanced aquifer remediation is proposed as technology to treat these sites. However, the polluted emulsion generated must be manged on-site. In this work a two-step process is applied to treat emulsion composed of E-Mulse® 3 (4 g·L−1) as surfactant and a DNAPL (2 gCOCs·L−1). In the first, the COCs were selectively adsorbed in a granular activated carbon (GAC) column with Fe (II) previously adsorbed (10–20mg·g-1) onto the carbon surface, recovering an aqueous phase with surfactant for their reuse. In the second step, the spent GAC was regenerated with a 40 g·L−1 solution of hydrogen peroxide fed to the column at 2 mL·min−1 to promote the oxidation of the COCs adsorbed in the GAC. The kinetic and adsorption model in a multisolute (surfactant and DNAPL) system has been proposed. Five successive cycles of regeneration/adsorption have been successfully applied in the column process. About 50 % of the COCs were retained from the emulsion, and more than 70 % of the surfactant was recovered. The consumption of unproductive oxidants decreased with the number of regeneration cycles. The water effluent obtained after regeneration of GAC did not present chlorinated compounds desorbed and nontoxic by-products generated, such as short-chain acids.

Remediation of groundwater polluted with lindane production wastes by conductive-diamond electrochemical oxidation

This work studies the remediation of groundwater saturated with dense non-aqueous phase liquid (DNAPL) from lindane production wastes by electrochemical oxidation. DNAPL-saturated groundwater contains up to 26 chlorinated organic compounds (COCs), including different isomers of hexachlorocyclohexane (HCH). To do this, polluted groundwater was electrolysed using boron-doped diamond (BDD) and stainless steel (SS) as anode and cathode, respectively, and the influence of the current density on COCs removal was evaluated in the range from 5 to 50 mA cm−2. Results show that current densities higher than 25 mA cm−2 lead to the complete removal and mineralisation of all COCs identified in groundwater. The higher the current density, the higher the COCs removal rate. At lower current densities (5 mA cm−2), chlorobenzenes were completely removed, and degradations above 90 % were reached for COCs with more than five chlorine atoms in their molecules. The use of BDD anodes promotes the electrochemical generation of powerful reactive species, such as persulfate, hypochlorite or hydroxyl radicals, that contribute to the degradation and mineralisation of COCs. The applied current density also influences the generation of these species. Finally, no acute toxicity towards Vibrio fischeri was observed for the treated groundwater after the electrochemical oxidation performed at 5 and 10 mA cm−2. These findings demonstrate that electrochemical oxidation with BDD anodes at moderate current densities is a promising alternative for the remediation of actual groundwater contaminated with DNAPLs.

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 %.

Removal of organochlorine pollutants from DNAPL-saturated groundwater using electrolysis with MMO anodes

This work evaluates the electrolysis of groundwater saturated with dense non-aqueous phase liquid (DNAPL) from lindane production wastes using mixed metal oxide (MMO) anodes to remove 26 Chlorinated Organic Compounds (COCs). Synthetic groundwater saturated with DNAPL from an industrial landfill was employed, and the influence of the current density (5–50 mA cm−2) was studied. Results show that removing COCs from DNAPL-saturated groundwater in 300 min is possible, reaching a final conversion of 0.99 when current densities of 50 mA cm−2 are applied. Under these operating conditions, the mineralisation conversion achieved is above 0.80. Low molecular weight COCs are rapidly oxidised because the evaporation also contributes to decrease their concentration in groundwater. Chlorine-based electrogenerated oxidants are the main species responsible for the removal of COCs. Toxicity and biodegradability tests performed on treated groundwater reveal that EC50 increases above 65 %, and 100 % biodegradability is obtained. The highest energy efficiencies are obtained during the treatment at 5 mA cm−2 (over 0.03 m3 kW-1h−1 for all COCs) due to the minimisation of parallel oxidation reactions promoted at higher current densities.

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.

Enhancing remediation of residual DNAPL in multilayer aquifers: Post-injection of alcohol-surfactant-polymer mixtures

Although polymer-surfactant injection is an effective remediation technology for multilayer aquifers contaminated by Dense Non-Aqueous Phase Liquids (DNAPL), the existence of residual DNAPL after treatment is inevitable. This study evaluates the efficiency of the post-injection of alcohol-surfactant-polymer (ASP) mixtures containing 1-propanol/1-hexanol, sodium dodecylbenzenesulfonate (SDBS), and xanthan in enhancing remediation of residual DNAPL in layered systems. A range of experimental devices, including batch, rheological measurements, centimetric 1D column, and decametric 2D tank experiments, were employed.Batch experiments revealed that the inclusion of 1-hexanol swelled the DNAPL volume due to alcohol partitioning. Conversely, with only 1-propanol present in the alcohol-surfactant (AS) mixture, DNAPL dissolved in the aqueous phase. The co-presence of 1-hexanol along with 1-propanol in AS mixture favored 1-propanol's partitioning into the DNAPL phase.Column experiments, following primary xanthan-SDBS (XS) injections, demonstrated that ASP mixtures with 1-hexanol (regardless of presence of 1-propanol) underwent a mobilization mechanism. DNAPL appeared in the effluent as an organic phase after the post-injection of 0.3 pore-volumes (PV), by a reduction trend in its density. In contrast, mixtures with solely 1-propanol exhibited a solubilization mechanism, with DNAPL dissolving in the aqueous phase and emerging in the effluent after approximately 1 PV.2D tank experiments visualized mobilization and solubilization mechanisms in multilayered systems. Post-injection of the ASP mixture with solely 1-propanol led to DNAPL solubilization, demonstrated by a dark zone of varied DNAPL concentrations, followed by a clearer white zone indicating significant DNAPL dissolution. Injecting ASP mixture containing both 1-propanol and 1-hexanol mobilized swollen DNAPL ganglia throughout layers, with these droplets coalescing and migrating to the recovery point. The darkness of mobilized droplets was faded as more DNAPL was recovered. The solubilization ASP mixture enhanced the recovery factor by 0.02 while the mobilization ASP mixture led to a 0.08 increase in the recovery factor.

Improved ERT imaging with 3-D surface-to-horizontal borehole configurations: relevance to dense non-aqueous phase liquids

SUMMARY Accurate characterization and monitoring strategies are essential for designing and implementing remedial programs for sites polluted with dense non-aqueous phase liquids (DNAPLs). Electrical resistivity tomography (ERT) is a widely used geophysical technique for mapping subsurface features and processes of interest, and exhibits desirable characteristics for DNAPL sites due to its ability to gather large volumes of continuous subsurface information in a non-invasive, cost-effective and time-efficient manner. However, ERT measured only from the surface suffers from poor imaging quality with depth. Enhanced ERT imaging can be obtained via electrodes deployed on the surface and within horizontal boreholes, but so far it has only been investigated for 2-D imaging. This study evaluates the potential of 3-D surface-to-horizontal borehole (S2HB) ERT configurations for imaging 3-D DNAPL source zones. Laboratory tank experiments were first conducted with a 3-D S2HB ERT configuration, which consisted of a surface grid and a single borehole line of electrodes, being used to monitor DNAPL migration within porous media. Results demonstrate that 3-D S2HB ERT with a single borehole provides improved sensitivity at depth, and therefore enhanced imaging compared to conventional 3-D surface ERT. Further tank experiments were performed to assess the performance of single borehole S2HB ERT when (i) the distance between surface and borehole is increased, and (ii) additional horizontal boreholes are included. The S2HB ERT with a single borehole significantly outperforms surface ERT at larger depths, and performs comparably to S2HB ERT using multiple boreholes. This study suggests that 3-D S2HB ERT with a single borehole can provide the enhanced imaging ability needed to map DNAPLs, while also being relatively practical for implementation at field sites.

Critical review of the environmental management of a DNAPL contaminated site in Resende, Rio de Janeiro, Brazil

The current nonconformity of most Brazilian states regarding the environmental guidelines established by the Conama 420 resolution makes clear that there are still many challenges to be faced on the management field of contaminated sites. The analysis of a factual remediation operation in an industrial site in the city of Resende, Rio de Janeiro state, show that traditional site investigation techniques are still being applied as main tools of characterization, data collection and decision-making in the management of the area. The site has had its investigation start in the late 90’s through multiple soil sampling and monitoring wells installation, pointing DNAPLs (dense non-aqueous phase liquids) among the chemicals of interest. The industrial site has undergone remediation for over 10 years now and has not been closed yet. More recently, the efficiency reduction of the primary remediation system, a dual-phase extraction system with over 50 installed wells, led to the implementation of in-situ stimulated bioremediation. Performance reports show lower efficiency than expected, hinting that a lackluster CSM (conceptual site model) might be leading to poor decision making. Despite being adequate remediation techniques, previous efforts and literature indicate that the site must undergo new investigation steps employing high-resolution site characterization (HRSC) techniques such as the MIP (membrane interface probe), allowing the refinement of the current CSM and the optimization of current remediation efforts.

Stratified migration and distribution of the constituents of coal tar in the stratum

Coal tar (CT) is widely used in the rubber industry to produce a reinforcing substance known as carbon black. Due to the complexity constituents of CT, the migratory dynamics of its constituents have not been characterized, resulting in contamination of soil and groundwater. To understand the migration and distribution characteristics of different nature components of CT in the study site, the distribution and migration patterns of total petroleum hydrocarbons (TPHs), polycyclic aromatic hydrocarbons (PAHs), and Dense Non-Aqueous Phase Liquids (DNAPLs, ρ≫1 g/cm³) in soil and groundwater in a rubber enterprise were characterized and analyzed. We found that: the different components in CT settle at different points in the soil as they migrate, exhibiting stratification. Specifically, TPHs in soil and groundwater are mainly concentrated in the shallow layer near the tank area, and the maximum concentration is 113,000 mg/kg; PAHs are more migratory than TPHs, and the maximum concentration of PAHs is 7408 mg/kg. Most PAHs are concentrated in the middle layer and above; DNAPLs tend to be transported to deeper stratum, penetrating deeper into the terrain and aggregating into pools (depth＞13 m). In addition, the inherently slow flow of groundwater slower groundwater flow does not significantly impact the further migration of pooled DNAPLs, but it does influence the orientation of their pollution plume. This study provides a more accurate characterization of the dynamics of pollutants associated with rubber enterprises; these results bring forth a theoretical basis for the remediation and management of pollution linked with CT.

Performance evaluation of surrogate models for simulating multiphase NAPL transport in heterogeneous aquifers

Abstract A better understanding of the distribution of nonaqueous phase liquid (NAPL) plumes is of great importance to groundwater pollution remediation and control. However, the efficiency of surrogate models in simulating the transport is still not well addressed. Selecting a leakage problem as an example, 50 sets of random permeability distributions are generated using the Monte Carlo method, and a numerical model is used to obtain benchmark data of NAPL transport. Four machine learning methods are employed to simulate dense NAPL transport under point leakage sources across spatiotemporal scales. The validation of the models demonstrate that the random forest model can also effectively capture the spatial-temporal distribution of the plume in heterogeneous aquifers, with a maximum mean absolute error and root mean square error smaller than 5.55 × 10−4 and 5.88 × 10−5, respectively. Meanwhile, the multiple phase outcome from the random forest model fits well with the numerical results under the scenarios of linear leakage sources and light NAPL transport. The total time consumed in the computation is reduced by over 150 times after using the surrogate models. The results suggest that surrogate models can provide a promising way to understand NAPL transport in heterogeneous aquifers.