Dense Non-aqueous Phase Liquid Migration Research Articles

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.

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.

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.

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.

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.

The Effects of Spill Pressure on the Migration and Remediation of Dense Non-Aqueous Phase Liquids in Homogeneous and Heterogeneous Aquifers

The spill pressure of the contaminant source is an important factor affecting the amount, location, form, and behavior of the dense non-aqueous phase liquids (DNAPLs) that plume in a contaminated subsurface environment. In this study, perchloroethylene (PCE) infiltration, distribution and, remediation via a surfactant-enhanced aquifer remediation (SEAR) technique for a PCE spill event are simulated to evaluate the effects of the spill pressure of the contaminant source on the DNAPLs’ behavior in two-dimensional homogeneous and heterogeneous aquifers. Five scenarios with different spill pressures of contamination sources are considered to perform the simulations. The results indicate that the spill pressure of the contaminant source has an obvious influence on the distribution of DNAPLs and the associated efficiency of remediation in homogeneous and heterogeneous aquifers. As the spill pressure increases, more and more contaminants come into the aquifer and the spread range of contamination becomes wider and wider. Simultaneously, the remediation efficiency of contamination also decreases from 93.49% to 65.90% as the spill pressure increases from 33.0 kPa to 41.0 kPa for a heterogeneous aquifer with 200 realizations. The simulation results in both homogeneous and heterogeneous aquifers show the same influence of the spill pressure of the contaminant source on PCE behaviors in the two-dimensional model. This study indicates that the consideration of the spill pressure of the contaminant sources (such as underground petrol tanks, underground oil storage, underground pipeline, and landfill leakage) is essential for the disposal of contaminant leakage in the subsurface environment. Otherwise, it is impossible to accurately predict the migration and distribution of DNAPLs and determine the efficient scheme for the removal of contaminant spills in groundwater systems.

Three-Dimensional High-Precision Numerical Simulations of Free-Product DNAPL Extraction in Potential Emergency Scenarios: A Test Study in a PCE-Contaminated Alluvial Aquifer (Parma, Northern Italy)

Chlorinated organic compounds are widespread aquifer contaminants. They are known to be dense non-aqueous phase liquids (DNAPLs). Therefore, they are denser than water and immiscible with other fluids. Their migration into the environment in variably saturated zones can cause severe damage. For this reason, optimizing those actions that minimize the negative impact of these compounds in the subsurface is essential. This paper presented a numerical model simulating the free-product DNAPL migration and extraction through a purpose-designed pumping well in a potential emergency scenario. The numerical simulations were performed using CactusHydro, a numerical code that uses a high-resolution shock-capturing flux conservative method to resolve the non-linear coupled partial differential equations of a three-phase immiscible fluid flow recently proposed in the literature, including the contaminant extraction at the base of the aquifer. We investigated the temporal (and spatial) evolution of its migration in the Parma (Northern Italy) porous alluvial aquifer following the saturation contour profiles of the three-phase fluid flow in variably saturated zones. The results indicated that this numerical approach can simulate the contaminant migration in the subsurface and the pumping of the free-product from a well screened at the base of the aquifer system. Moreover, the simulation showed the possibility of recovering about two-thirds of the free-product, in agreement with the scientific literature.

Migration of DNAPL in Saturated Porous Media: Validation of High-Resolution Shock-Capturing Numerical Simulations through a Sandbox Experiment

This paper shows a comparison between experiments carried out in a laboratory-scale sandbox where the migration of a dense nonaqueous phase liquid (DNAPL), hydrofluoroether (HFE-7100), in a saturated porous medium was investigated, and validation was performed using high-resolution shock-capturing numerical simulations to resolve the nonlinear governing coupled partial differential equations of a three-phase immiscible fluid flow. The contaminant was released using a colored fluid as a tracer for a fixed time and pressures different from the atmospheric one into the saturated zone, first by using a column laboratory experiment, and then a sandbox-scale example with a hydraulic gradient. A digital image analysis procedure was used to determine the saturation distribution of the contaminant during its migration. These results are compared with the values determined for a DNAPL migration in a similar porous media through a numerical simulation. They show good agreement with the experimental results and also show that CactusHydro can follow the migration of a plume evolution very precisely and can also be used to evaluate the effects and environmental impacts deriving from leaks of DNAPL in saturated zones.

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.

Experimental Study on Residual and Dissolution of DNAPL in Transparent Fracture

Dense nonaqueous phase liquid (DNAPL) is one of the main pollution sources of the underground environment. After DNAPL enters the underground environment, the migration and diffusion process has experienced a variety of media, resulting in large-scale and long-term pollution. To better understand the residual and dissolution process of DNAPL in fractures, the visual experiment of DNAPL residual and dissolution in the fracture was carried out using the transparent fracture model made of glass material, and the changes of DNAPL migration morphology and residual distribution in the crack were obtained. The results showed that the migration front of DNAPL in the fracture was finger shaped in the process of displacement of water phase by DNAPL phase, which was consistent with the state in porous media. When the process of water phase displacing DNAPL phase was over, discrete and aggregated DNAPL droplets remained in the fracture. The residual DNAPL was mainly concentrated in the area ranged from 0.3 mm to 0.8 mm. The dissolution rate of DNAPL in the fracture changed from fast to slow, and there was an obvious tailing period. The increased velocity of water phase flow significantly shortened the time of dissolution process. The DNAPL with hydrolysis reaction accounted for only 0.86% on average in the dissolution process. The findings of this study are helpful to the remediation of the underground environment.

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.

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.

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.

A study of the influencing factors of DNAPLs transport in stochastic network fractures

The migration and distribution of dense non-aqueous phase liquid (DNAPLs) in fractured media are affected by many factors, including the physical and chemical properties of DNAPLs, geometric and chemical properties of fractures and leakage conditions. Previous studies were mostly conducted in a single fracture, while the migration of DNAPLs in stochastic network fracture were seldom examined. In this paper, stochastic network fractures are generated using the Monte Carlo method. The coordinates and apertures of fractures are identified and output by pixel scanning. The migration of Perchloroethylene (PCE) in the stochastic network fractures is simulated by PetraSim. The effects of the geometric properties of the fractures and the leakage conditions (including the leakage rate and the leakage location) on the migration of DNAPLs are discussed. The numerical simulation results show that the spatial variability of fractures also affects the migration path and spatial distribution of DNAPLs. With the increase of spatial variability of fracture width in the network fractures, dominant channels appear, the migration rate of DNAPLs accelerates, and the location of DNAPLs centroid and the spatial distribution of saturation change significantly. The leakage rate affects the migration range and spatial distribution of DNAPLs. The higher the leakage rate is, the faster the migration rate of DNAPLs will be. The more saturated the accumulated DNAPLs at the bottom of the model, the greater the spatial distribution of DNAPLs is. In the same network fracture, different leakage locations will also lead to different migration paths and distribution ranges of DNAPLs. The spatial variability of fractures in the gravity direction at different leakage locations is different, leading to different migration paths and spatial distribution of DNAPLs.

Aquifer flushing using a SDS/1-butanol based in-situ microemulsion: Performance and mechanism for the remediation of nitrobenzene contamination

In-situ microemulsion flushing is an effective remediation technology for the removal of dense non-aqueous phase liquids (DNAPLs) from aquifers. Nitrobenzene (NB) is a typical DNAPL pollutant that is responsible for the serious contamination of many groundwater systems, while its removal using the flushing method has rarely been studied. In this study, bench scale, 1-D column and 2-D tank experiments were conducted to establish an efficient salt-free sodium dodecyl sulfate (SDS)/1-butanol based in-situ microemulsion flushing system for NB contaminated aquifers. Results showed that the NB/SDS/1-butanol/water microemulsion increased dissolved NB concentrations by more than 15-fold compared to the SDS-only solution. The formulation also presented good solubilization capacity at low temperature (5 ℃) and with clay media. NB was effectively removed from the aquifer by solubilization and mobilization via the formation of the microemulsion with the injected SDS/1-butanol solution. The flushing system also reduced the tailing phenomenon in later remediation stages, and exhibited weak reagent adsorption onto aquifer media. Furthermore, the vertical DNAPL migration to deeper aquifer was effectively controlled. Therefore, the constructed in-situ microemulsion flushing system is a highly efficient treatment method for NB contaminated aquifers, with this study providing valuable reference information on the optimal reagent parameters and the remediation mechanism.

Mechanisms of irreversible density modification using colloidal biliquid aphron for dense nonaqueous phase liquids in contaminated aquifer remediation

The use of colloidal biliquid aphron (CBLA) as density modifier to reduce the density of dense nonaqueous phase liquids (DNAPLs) irreversibly is an efficient strategy to control the migration of DNAPLs in contaminated aquifers. However, the process and mechanism of the density regulation using CBLA is still not clear and there is still a big gap in the application of CBLA in actual contaminated sites. In this study, we carried out density modification of 5 DNAPLs (nitrobenzene (NB), dichloromethane (DCM), trichloroethylene (TCE), carbon tetrachloride (CTC), perchloroethylene (PCE)) using CBLA and studied the effect of co-existing ions by 3D response surface method. We found that DNAPLs changed to light nonaqueous phase liquids (LNAPLs) and float up after interaction with light organic liquid from CBLA. The density modification process is limited by the demulsificaiton of CBLA and the density of DNAPL itself. Density regulation of DNAPLs followed pseudo-second-order kinetics. The co-existing ions affected the stability of CBLA and the demulsification ability of the demulsifier. Aquifer materials and low temperature did not influence the density control effect of CBLA. This research advances the practical application of density control of DNAPLs using CBLA, and makes important contributions for subsequent combined remediation approach.

Towards predicting DNAPL source zone formation to improve plume assessment: Using robust laboratory and numerical experiments to evaluate the relevance of retention curve characteristics

We conducted multiple laboratory trials in a robust and repeatable experimental layout to study dense non-aqueous phase liquid (DNAPL) source zone formation. We extended an image processing and analysis framework to derive DNAPL saturation distributions from reflective optical imaging data, with volume balance deviations < 5.07%. We used a multiphase flow model to simulate source zone formation in a Monte Carlo approach, where the parameter space was defined by the variation of retention curve parameters. Integral and geometric measures were used to characterize the source zones and implemented into a multi-criteria objective function. The latter showed good agreement between observation data and simulation results for effective DNAPL saturation values > 0.04, especially for early stages of DNAPL migration. The common hypothesis that parameters defining the DNAPL-water retention curves are constant over time was not confirmed. Once DNAPL pooling started, the optimal fit in the parameter space was significantly different compared to the earlier DNAPL migration stages. We suspect more complex processes (e.g., capillary hysteresis, adsorption) to become relevant during pool formation. Our results reveal deficits in the grayscale-DNAPL saturation relationship definition and laboratory estimation of DNAPL-water retention curve parameters to overcome current limitations to describe DNAPL source zone formation.

The role of surfactants in colloidal biliquid aphrons and their transport in saturated porous medium

In remediation of dense non-aqueous phase liquids (DNAPLs), colloidal biliquid aphrons (CBLAs) could be added to produce a lower density nonaqueous phase which mitigate downward migration of DNAPL to non-polluted aquifers. There is still a big gap in the application of CBLAs in the remediation of actual polluted sites, especially the absence of relevant studies on its transport behavior in the sites, and its structural model has not been fully verified. These two factors could affect the effectiveness of CBLAs in the underground environment and its effect on density control. In this study, we prepared CBLAs with different surfactants and verified the structural model of CBLA based on their particle size distributions and demulsification performance. We studied the effects of particle concentrations, injection velocities, and porous media size on the migration of CBLA using the breakthrough curves and distribution profiles along the column. Experimental results indicated that surface elasticity of CBLAs was inversely proportional to the concentration of the anionic surfactant sodium dodecyl sulphate (SDS), which led to easier demulsification of CBLA with the increase in SDS concentration. This observation was in agreement with the verified structural model of the CBLA which constitute both internal nonionic and external anionic surfactants. Furthermore, CBLA deposition is mainly caused by interception and is not suitable for application in fine media. Low concentration of CBLA and high injection flow rate help CBLA to form a remediation area with a certain radius. This study solved the problem of DNAPLs in contaminated groundwater from the perspective of density regulation, and made contributions towards the development of combined remediation approaches using CBLAs.

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.