Non-aqueous Phase Liquid Contamination Research Articles

Effects of mono- and multicomponent nonaqueous-phase liquid on the migration and retention of pollutant-degrading bacteria in porous media

The successful implementation of in-situ bioremediation of nonaqueous-phase liquid (NAPL) contamination in soil-groundwater systems is greatly influenced by the migration performance of NAPL-degrading bacteria. However, the impact and mechanisms of NAPL on the migration/retention of pollutant-degrading bacteria remain unclear. This study investigated the migration/retention performance of A. lwoffii U1091, a strain capable of degrading diesel while producing surfactants, in porous media without and with the presence of mono- and multicomponent NAPL (n-dodecane and diesel) under environmentally relevant conditions. The results showed that under all examined conditions (5 and 50 mM NaCl solution at flow rates of 4 and 8 m/d), the presence of n-dodecane/diesel in porous media could reduce the migration and enhance retention of A. lwoffii in quartz sand columns. Moreover, comparing with mutlicomponent NAPLs of n-dodecane, the monocomponent NAPLs (diesel) exhibited a greater reduction effect on the retention of A. lwoffii in porous media. Through systemically investigating the potential mechanisms via tracer experiment, visible chamber experiment, and theoretical calculation, we found that the reduction in porosity, repulsive forces and movement speeds, the presence of stagnant flow zones in porous media, particularly the biosurfactants generated by A. lwoffii contributed to the enhanced retention of bacteria in NAPL-contaminated porous media. Moreover, owing to presence of the greater amount of hydrophilic components in diesel than in n-dodecane, the available binding sites for the adsorption of bacteria were lower in diesel, resulting in the slightly decreased retention of A. lwoffii in porous media containing diesel than n-dodecane. This study demonstrated that comparing with porous media without NAPL contamination, the retention of strain capable of degrading NAPL in porous media with NAPL contamination was enhanced, beneficial for the subsequent biodegradation of NAPL.

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 %.

Larger aggregate formed by self-assembly process of the mixture surfactants enhance the dissolution and oxidative removal of non-aqueous phase liquid contaminants in aquifer

Surfactants can transfer non-aqueous phase liquid (NAPL) contaminants to the aqueous phase, and enhance the removal of the latter in groundwater. However, the extensive use of surfactants causes secondary contamination and increases the non-target consumption of oxidants. It is pressing to develop a surfactant with high phase transfer efficiency and sound compatibility with oxidants to minimize the use of surfactants for groundwater remediation. The phase transfer capability of different surfactants and their binary mixtures, their enhanced KMnO4 oxidation performance for NAPL contaminants as well as influencing factors were investigated to solve the above-mentioned question. The results showed that Tween20, SDBS and BS-12 perform best in terms of phase transfer capability among nonionic, anionic and amphoteric surfactants respectively, and only SDBS and BS-12 produce a synergistic effect among the binary mixtures. The CMC of SDBS/BS-12 was lower than its ideal CMC value, and the self-assembly process of SDBS/BS-12 also formed larger aggregates, which improved the phase transfer performance. Compared to other single surfactants, the removal efficiency of petroleum hydrocarbons in the aquifer sediments was raised by 7.4–33.8 % using the mixed surfactant. The SDBS/BS-12 mixture was compatible with KMnO4 and boosted the reaction of NAPL contaminants with KMnO4 by transferring from the NAPL phase to the aqueous phase. As a result, the NAPL toluene and phenanthrene removal efficiency increased from 37 % and 29 % to 80 % and 86 % respectively. Natural organic matters inhibited the phase transfer efficiency of the SDBS/BS-12 mixture, whereas anions and monovalent cations enhanced the phase transfer capability of the mixture. High-valent cations led to precipitation in the SDBS/BS-12, which could be eliminated by adding Na2Si2O5. The SDBS/BS-12 mixture delivered the same phase transfer efficiency with the dosage of 1.73–23.07 % of other single surfactants, and its cost was equivalent to 0.25–41.7 % of the latter, thus embracing bright application prospects.

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

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

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

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

Encapsulation of zero valent iron nanoparticles in biodegradable amphiphilic janus particles for groundwater remediation

Reactive Zero Valent Iron (ZVI) nanoparticles have been widely explored for in situ ground water remediation to degrade both non-aqueous phase liquid (NAPL) and water-soluble contaminants. However, they usually suffer from rapid oxidation and severe agglomerations restricting their delivery at NAPL/water interface. Aim of this study was to encapsulate the ZVI nanoparticles (50 nm) in amphiphilic bicompartmental Janus particles (711 ± 11 nm) fabricated by EHDC (electrohydrodynamic co-jetting). The dual compartments were composed of PLA (polylactic acid) and a blend of PLA, PE (poly (hexamethylene 2,3-O-isopropylidenetartarate) and PAG (photo acid generator). Upon UV irradiation, PAG releases acid to unmask hydroxyl groups present in PE to make only PE compartment hydrophilic. The entrapped ZVI nanoparticles (20 w/w%; ∼99 % encapsulation efficiency) were observed to degrade both hydrophilic (methyl orange dye) and hydrophobic (trichloro ethylene) contaminants. UV treated Janus particles provided stable dispersion (dispersed up to 3 weeks in water), prolonged reactivity (∼24 days in contaminated water), and recyclability (recyclable up to 9 times) as compared to non-treated ones. In addition, the amphiphilic Janus particles demonstrated high transportability (>95%) through porous media (sand column) with very low attachment efficiency (0.07), making them a promising candidate to target contaminants at NAPL/water interface prevailed in groundwater.

An approach for quantification of the heterogeneity of DNAPL source zone geometries

Many studies have investigated the migration and entrapment processes of source zones from dense non-aqueous phase liquid (DNAPL) contamination under different conditions. However, the characterization of occupying area by source zone (or source shape) in water-saturated aquifers is still rudimentarily considered. In this study, we demonstrated this issue (1) by providing a brief review of existing approaches for source shape consideration, (2) by proposing an approach with simple shape parameters based on the non-uniformity of source widths, and (3) by providing exemplary applications of our proposed approach on shapes already published in previous research works. Our literature review suggested that the source zone in mathematical approaches is generally characterized as simple geometrical shapes (arbitrary lines or rectangles) or system-defined parameters that contrast to complex and discontinuous shapes observed in the real world. But the characterization of such complex shapes is still not possible with acceptable efforts. Therefore, we proposed an approach to parameterize the source shape by considering the variation of width and midpoints over the depth of the entire source zone and formulate four parameters based on population statistics (mean, standard deviation). To illustrate the suitability of our approach, we applied it to the results of lab experiments, and by analyzing these complex shapes, we highlighted the potential for improving the characterization techniques of non-uniformity of the source zones.

Coupling surfactants with ISCO for remediating of NAPLs: Recent progress and application challenges.

Non-aqueous phase liquids (NAPLs) pose a serious risk to the soil-groundwater environment. Coupling surfactants with in situ chemical oxidation (ISCO) technology is a promising strategy, which is attributed to the enhanced desorption and solubilization efficiency of NAPL contaminants. However, the complex interactions among surfactants, oxidation systems, and NAPL contaminants have not been fully revealed. This review provides a comprehensive overview on the development of surfactant-coupled ISCO technology focusing on the effects of surfactants on oxidation systems and NAPLs degradation behavior. Specifically, we discussed the compatibility between surfactants and oxidation systems, including the non-productive consumption of oxidants by surfactants, the role of surfactants in catalytic oxidation systems, and the loss of surfactants solubilization capacity during oxidation process. The effect of surfactants on the degradation behavior of NAPL contaminants is then thoroughly summarized in terms of degradation kinetics, byproducts and degradation mechanisms. This review demonstrates that it is crucial to minimize the negative effects of surfactants on NAPL contaminants oxidation process by fully understanding the interaction between surfactants and oxidation systems, which would promote the successful implementation of surfactant-coupled ISCO technology in remediation of NAPLs-contaminated sites.

Emergence of non-aqueous phase liquids redistribution driven by freeze-thaw cycles in porous media based on low-field NMR

• Redistribution of NAPLs driven by freeze–thaw (FT) cycles was confirmed in a wide saturation range (14.34% to 72.05%). • Substantial remobilization of NAPLs occurred between macropores and mesopores during FT cycles. • Distribution of NAPLs in micropores remained almost unchanged during FT cycles. • Contribution of micropores to NAPLs redistribution was much smaller than that of mesopores and macropores. • A model related to freezing-induced pressure was proposed to explain the change in the redistribution rate of NAPLs. Increasing human activities in cold regions have led to serious environmental problems due to non-aqueous phase liquids (NAPLs) contamination. However, the NAPLs redistribution driven by freeze–thaw (FT) cycles is not well understood. In this study, the redistribution of NAPLs in porous media subjected to FT cycles in a temperature range from 20 °C to −15 °C was investigated using the low-field Nuclear Magnetic Resonance (NMR) technique. The redistribution of NAPLs in the prepared samples with NAPLs saturation ranging from 13.56% to 72.05% was confirmed using the transverse spin-spin relaxation time ( T 2 ) distribution and the magnetic resonance imaging (MRI). Experimental results revealed that substantial remobilization and distribution of NAPLs occurred between the macropores ( T 2 greater than 300 ms) and the mesopores (60 ms < T 2 < 300 ms) while the NAPLs in the micropores ( T 2 < 60 ms) remained almost unchanged during 30 FT cycles. The main reason is attributed to the fact that the redistribution rate in micropores is much lower than in macropores and mesopores. Furthermore, the NAPLs content and the number of FT cycles were positively correlated for macropores while negatively correlated for mesopores. For the samples with low NAPLs saturation (e.g., S N =13.56% and 13.56%), the redistribution rate of NAPLs versus FT cycles exhibited an overall linear relationship for macropores and mesopores while a non-liner relationship for micropores. For all pore categories, the increment in S N can cause a remarkable deviation extent. The balance between capillary pressure and freezing-induced pressure was evaluated by the newly introduced dimensionless pressure ratio Δ P , which could help determine the ultimate mobilization and redistribution of NAPLs during FT cycles. Experimental tests suggested that the Δ P was much larger in macropores than in mesopores and micropores. This can explain the dramatic difference in the redistribution rate among different pore categories. This fundamental study is helpful in understanding the mobilization and redistribution mechanisms of NAPLs in cold regions.

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.

Aquifer remediation using surfactant-enhanced gas sparging applied to target the contaminant source

The surfactant-enhanced gas sparging process designed to specifically target the source zone of an organic contaminant in an aquifer with minimal usage of injected additives was investigated using a physical model. Aqueous solutions of the anionic surfactant Sodium dodecylbenzne sulfonate (SDBS) and/or the thickener Sodium carboxymethylcellulose (SCMC) were applied in a contaminated horizontal layer in the simulated laboratory aquifer model followed by gas sparging. Fluorescein sodium salt (FSS) was added to the SDBS/SCMC solutions and represented the organic contaminant. Air and ozone were injected to generate gas sparging. A modified surfactant-enhanced ozone sparging method was also tested by applying additional air venting ports installed in the aquifer above the gas injection zone. Both non-aqueous phase liquid (NAPL) and water-dissolved TCA were applied to the SDBS-applied region to evaluate the removal of contaminants during gas sparging. A significant expansion of the de-saturated zone for the SDBS-applied region was observed during air sparging. During ozone sparging, the fluorescence by FSS in the SDBS-applied layer disappeared over a much wider range than that of the control experiment. SCMC application enhanced the performance of the SDBS-applied gas sparging process. The TCA mass removed by volatilization during air sparging from the SDBS-applied layer was 2.3 times the application in the absence of SDBS. Among five regions of injected NAPL contamination located above the single gas injection port, and during 2 h of ozone sparging, with SDBS applied, more than 50% of fluorescence in the NAPL was removed, whereas under the same conditions with no SDBS applied, less than 30% was removed. Diverted gas flow through the venting ports installed in the aquifer model induced a horizontally expanded oxidative reaction zone during ozone sparging. This study demonstrates enhanced gas sparging performance for the removal of contaminants from the aquifer with limited usage of additives applied specifically to the source zone.

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

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

Application of Solid Phase Extraction (SPE) Media Rods to Assess Degree of NAPL Encapsulation in In Situ Deposited NAPL Sediments

ABSTRACT Oil-particle aggregates (OPAs) develop from solid particles attaching to and/or penetrating into the surface of a non-aqueous phase liquid (NAPL) bead suspended in the water column. In situ deposited NAPL (IDN) sediments result from the deposition of OPAs on the sediment bed at the bottom of the water body. The extent of solid particle coverage on the surface of the oil bead defines the degree of encapsulation of the OPA (i.e., fully or partially encapsulated). Since important properties such as NAPL mobility and contaminant flux are controlled by the degree of OPA encapsulation, the ability to measure this physical property is critical in characterizing NAPL fate and transport in IDN sediments. This paper describes a semi-quantitative method to measure the degree of encapsulation within IDN sediment using the fluorescence response from rods coated with solid phase extraction (SPE) media. Specifically, Direct Analysis in Real Time (DART®) technology, which was developed and is distributed by Dakota Technologies, was applied to measure the amount of contact between the SPE material coated on a vertical rod and the PAHs contained in the NAPL found in the surrounding IDN sediment. Based on laboratory results in this paper, the magnitude of the fluorescence response correlates with the degree of encapsulation. For the single NAPL and various sediment combinations prepared in the laboratory for this study, fully (or nearly fully) encapsulated IDN sediments produced a DART® response below 15% reference emitter (%RE), a defined internal standard, whereas partially encapsulated IDN sediments produced a DART® response that was generally above 30%RE and as high as several thousand %RE. This difference in fluorescence response enables DART® technology to be applied as a line of evidence to determine the degree of NAPL encapsulation in an IDN sediment in field screening programs.

Modeling of soil gas radon as an in situ partitioning tracer for quantifying LNAPL contamination

In the last decades radon (Rn) has been widely proposed as a naturally occurring tracer for non-aqueous phase liquids (NAPL) in the soil. This work examines the feasibility of using soil gas data collected at some distance from the source zone for the application of the Rn deficit technique for the identification and quantification of NAPL contamination. To this end, we used a steady-state 1-D analytical solution that is based on a 3-layer model that allows to simulate the transport and distribution of Rn in the source zone, capillary fringe and overlying unsaturated soil. The analytical solution was first validated against a more detailed numerical model available in the literature. Then, a series of simulations were carried out to evaluate the vertical concentration profiles of Rn in soil gas above the source zone and in background location not impacted by NAPL. Simulation results showed that the parameters that most influence the migration and distribution of Rn in the subsurface are the distance of the soil gas probe from the source zone and, to a lower extent, the type of contamination (e.g. diesel or gasoline) and the soil type. On the basis of these results, we developed some easy-to-use nomographs to estimate the residual NAPL phase based on the observed radon deficit in soil gas and on the probe to source distance and soil and NAPL characteristics. According to the obtained results, the radon deficit technique results a feasible method for a qualitative identification of residual NAPL when radon in soil gas is measured at distances lower than 2 m from the contaminated zone. However, for an accurate quantitative estimation of the NAPL phase content, soil gas probes should be preferably located at distances lower than 1 m from the source zone.

Optimum concentration of fly ash nanoparticles to stabilize CO2 foams for aquifer and soil remediation

Contamination caused by non-aqueous phase liquids (NAPLs) in aquifers and soil is an important challenge that requires effective remediation techniques. One potential approach is through the use of CO2 foams to displace NAPLs from permeable media. CO2 foams generated only by surfactants are not stable enough for the efficient removal of NAPLs contamination. This shortcoming may be alleviated via the use of nanoparticles (NPs)-surfactant mixtures as a stabilizing agent. This work focuses on the evaluation of the optimum concentration of fly ash nanoparticles for stabilizing CO2 foam with the combined action of the surfactant. The performance of this foam is evaluated in remediating a contaminated 41 mm × 36 mm surrogate permeable medium in a microfluidic device. Mixtures of fly ash, a by-product of coal-burning power plants, and alpha-olefin sulfonate (AOS) and lauramidopropyl betaine (LAPB) surfactants are used to generate stable foams. The results show that a 1000 mg/L AOS-LAPB surfactant solution along with 1000 mg/L of fly ash NPs produces the best performance. Formation of deposits in the matrix is observed. These deposits, which are more prominent at higher NP concentrations, appear to adversely affect displacement, displacement efficiency and remediation of the medium. This study demonstrates that using fly ash nanoparticles and optimizing their concentration can effectively stabilize CO2 foams and improve the displacement efficiency for aquifer and soil remediation.

3D dynamic model empowering the knowledge of the decontamination mechanisms and controlling the complex remediation strategy of a contaminated industrial site

Knowledge of the geology and hydrogeology of the polluted site emblematize a key requirement for environmental remediation, through assembling and synthesizing findings from various sources of physical evidence. In an increasingly virtual era, digital and geo-referenced metadata may serve as tools for collecting, merging, matching, and understanding multi-source information. The main goal of this paper is to emphasize the significance of a 3D hydrogeochemical model to the portrayal and the understanding of contamination dynamics and decontamination mechanisms at a highly contaminated industrial site. Some remediation measures are active on-site, due to the evidence-based presence of chlorinated solvents in groundwater. These are attributable to a slow-release source of pollutants in the saturated zone associated with very low permeability sediments. Therefore, in this research, a new technique for the remediation of secondary sources of dense non-aqueous phase liquid (DNAPL) contamination was investigated for the first time on a full-scale application. The combination of groundwater circulation wells (IEG-GCW®) and a continuous electron donor production device was set up to boost in situ bioremediation (ISB). A multi-phase approach was followed handling and releasing data during various remediation stages, from site characterization via pilot testing to full-scale remediation, thus allowing users to monitor, analyze, and manipulate information in 3D space-time. Multi-source and multi-temporal scenarios reveal the impact of ongoing hydraulic dynamics and depict the decontamination mechanisms in response to the interventions implemented over time, by quantifying the overall performance of the adopted strategies in terms of removal of secondary sources of pollution still active at the site.

Experimental and numerical assessment of Light Non-Aqueous Phase Liquid (LNAPL) subsurface migration behavior in the vicinity of groundwater table

Groundwater contamination by constituents of hydrocarbon fluids may occur from the earth’s surface or subsurface. Key sources of contamination include spills and leakages from oilwells, underground storage tanks (USTs), and oil transport-tankers. These light non-aqueous phase liquid (LNAPL) contaminants pollute the soil and its continuous migration, may even end up contaminating aquifer systems. This highlights the need to understand the fate and migration behavior of LNAPL contaminants in the subsurface, especially in the unsaturated zone – with a view to limiting the contaminants transport. This study presents a numerical approach for describing and predicting the fate of LNAPL contaminant-transport in the subsurface. Multiphase flow concept was adopted, where two LNAPL phases – oil, and gas – were mainly considered. Diesel and crude oil are the hydrocarbon contaminants used, while unconsolidated sand was used as the porous matrix. Two contaminant flow scenarios were simulated experimentally — surface and subsurface imbibition. Mass balance equations and constitutive functions from the several important phenomena that influence LNAPL contaminant flow, in the subsurface, are discussed. Extended Darcy’s law in combination with van Genuchten model were applied in the 2D numerical model description for mass balance equation and constitutive relationship, respectively. The numerical simulation was executed using COMSOL Multiphysics® v. 5.5. The numerical simulation results showed a good correlation with the experimental results, and suggest that exposure time, fluid viscosity, density, contaminant supply, amount released, and the hydraulic properties of the porous matrix, are the most important parameters in LNAPL contaminant subsurface migration. This study thereby concludes that if the fluid thermodynamic properties and the hydraulic properties of the porous matrix are known, the numerical model can accurately predict the migration behavior of hydrocarbon contaminants. In that way, it becomes possible to effectively track oil-spills and leakages propagating into the vicinity of groundwater table and freshwater aquifer. The study outcome is useful in designing and implementing efficient hydrocarbon contamination remediation approaches and saving time by taking the right action.

Influence of aqueous film forming foams on the solubility and mobilization of non-aqueous phase liquid contaminants in quartz sands

At sites where aqueous film forming foams (AFFFs) are used for fire suppression or training activities, interactions between dissolved foam constituents and organic liquids could alter contaminant migration in the subsurface. In this study, batch reactor and column experiments were conducted to investigate the potential for AFFF solutions to enhance the solubility and mobility of three representative non-aqueous phase liquid (NAPLs), JP-4 jet fuel, trichloroethene (TCE), and tetrachloroethene (PCE). For AFFF concentrations up to 5% wt. (50,000 mg/L), aqueous solubilities of TCE and PCE increased by less than 50%, indicating the absence of micellar solubilization. However, NAPL-water interfacial tensions were reduced to less than 1.5 mN/m and resulted in accumulation of up to 2.25 mg/m2 of AFFF at the NAPL-water interface. To assess the potential for AFFF to mobilize residual (entrapped) NAPL at a field application rate of 3% wt. (30,000 mg/L), columns were packed with two size fractions of Ottawa sands (20–30 mesh and 60–80 mesh) that yielded residual NAPL saturations ranging from 11.7 to 17.6%. Following injection of 3 pore volumes of the 3% wt. AFFF solution, partial mobilization of residual NAPL was observed for PCE, TCE, and JP-4, with saturation reductions of 0.7 to 2% in 20–30 mesh and 0.3% to 1.3% in 60–80 mesh Ottawa sand. The columns were then flushed with an ultralow-IFT surfactant solution consisting of 4% wt. 1:1 Aerosol AY/OT, which resulted in nearly complete mobilization of the remaining residual NAPL. When NAPL desaturation curves were expressed in terms of the total trapping number (NT), the threshold value of NT required for NAPL mobilization by 3% wt. AFFF was approximately 2 × 10−5, consistent with previous studies. These findings demonstrate that AFFF solutions can lead to partial mobilization of residual NAPL, and that the total trapping number concept can be used to predict such behavior a priori. In addition, the observed IFT reductions are sufficient to alter NAPL accumulation and redistribution behavior in the subsurface through enhanced spreading above the water table (e.g., JP-4) or penetration into lower-permeability media (e.g., TCE, PCE).

The mechanism of NAPL layer formation in a microfluidic device with dual-permeability: experiments and numerical simulation

In-situ remediation is an important technique for non-aqueous phase liquid (NAPL) contamination remediation in soils. Understanding the formation and distribution of NAPL contaminated layers in heterogeneous soils is essential to propose cost-effective remediation methods. Therefore, a two-dimensional microfluidic device with dual permeability zones was designed to simulate the soil-groundwater system and experimentally investigated the formation process of the NAPL contamination layer. Numerical modeling of phase field coupled with laminar flow was used to simulate the distribution of NAPL in soil-groundwater system, and the formation of NAPL contamination layer under typical groundwater flow rate and wetting angle was evaluated. The NAPL in the low permeable zone formed a stable contamination layer, while the NAPL in the high permeable zone was washed out to varying degrees and mainly resided in the junction of high-low-permeability regions of the chip, with residues of 42.2% and 23.3% in the chip high permeable region at groundwater velocities of 6.17 m/d and 10.16 m/d, respectively, the numerical simulation results were consistent with the experimental observations. This retention was diminished in the high permeable zone as the NAPL-to-wall wetting angle increased. In addition, when the contact angle was increased from 33° (lipophilic) to 108° (hydrophilic), the residual NAPL content in the high permeable zone decreased from 48.86% to 28.22%. This paper provides a reliable visualizable experimental platform for the study of NAPL pollution formation at micro-scale in heterogeneous groundwater system, and lays a foundation for the subsequent optimization of the remediation strategy.

Radon as a Natural Tracer for Monitoring NAPL Groundwater Contamination

In this research, the radioactive noble gas radon was used as a tracer for Non-Aqueous Phase Liquids (NAPLs) contamination, since it is much more soluble in these substances than in air or water. Soil radon remains trapped within the NAPLs, resulting in a local reduction in the radon concentration within close proximity to the contaminated area. This technique was applied to a contaminated site in Roma (Italy). The main residual NAPLs are total hydrocarbons and methyl-tertiary-butyl ether (MTBE), a water-soluble additive. The monitoring activities included two sampling campaigns of groundwater from 18 wells in February and May 2020. Concentration maps were produced using radon data. The results show that the radon deficit traces the location of NAPLs in the fuelling station very well, with a residual source zone extending in a NNW-SSE direction. A good correspondence between a low amount of radon and a higher concentration of NAPLs was found. A reduction in the average amount of radon in the May 2020 survey indicated a stronger remobilization of NAPLs compared to that of the February 2020 monitoring campaign. The peaks of Volatile Organic Compounds (VOCs) detected between 8–9 and 11–12 m depths indicate the presence of residual blobs of NAPLs in the vadose zone of the aquifer.