Nonaqueous Phase Liquid Research Articles

Effect of Water Content on Light Nonaqueous Phase Fluid Migration in Sandy Soil

Contamination from light nonaqueous phase fluids (LNAPLs) and their derivatives during mining, production, and transportation has become a concern. Scholars have extensively studied LNAPL contamination, but the role of water content variation on its migration process in the unsaturated zone has not been sufficiently researched. The specific issue addressed in this study is the impact of water content on the migration of light nonaqueous phase liquids (LNAPLs) in sandy soils, a critical yet under-researched aspect of subsurface contamination. To tackle this, we employed indoor simulated vertical, one-dimensional, multiphase flow soil column experiments, utilizing the orthogonal experimental method to systematically evaluate the effects of varying water contents on the occurrence state and migration rate of LNAPLs. The experimental results indicate the following: (1) The migration rate of LNAPL exhibits an L-shaped trend during subsurface imbibition and a nonlinear relationship with migration time. The migration rate and migration time of surface infiltration have a linear growth relationship. (2) The residual rate of LNAPL is negatively correlated with water content and positively correlated with oil content in the homogeneous non-saturated state. With the increase in the amount of leaked oil, 40% of the leaked LNAPL is sorbed within the soil. (3) When the water content of the test medium is below 14%, and the oil content is below 11%, LNAPL appears in the unsaturated zone in a solid phase. As the water content increases, the adsorption rate of the oil phase gradually decreases and eventually reaches the oil saturation point. (4) When the water content of the medium exceeds 8%, over time, LNAPL will be subject to oil–water interfacial tension, and the rate of LNAPL movement first decreases and then increases, displaying nonlinear growth. The innovation of this work lies in the comprehensive analysis of LNAPL migration under controlled laboratory conditions, providing results that enhance the understanding of LNAPL behavior in sandy soils. These quantitative insights are crucial for developing targeted remediation strategies for LNAPL-induced pollution in the unsaturated zone.

Increasing LNAPL density and viscosity are indicators of Natural Source Zone Depletion

Natural source zone depletion (NSZD) acts to reduce the mass and/or toxicity of light non-aqueous phase liquids (LNAPL) in the shallow subsurface. Several indirect measurement techniques are commonly used to estimate LNAPL mass depletion based on CO 2 generation by hydrocarbon mineralisation, heat production by exothermic biodegradation processes, and sub-surface gas concentration gradients. This paper presents data on LNAPL density and viscosity and shows changes that result from NSZD processes. Increasing trends in LNAPL density and viscosity were observed that provided a qualitative line-of-evidence for NSZD. When LNAPL density and viscosity were combined with contemporaneous LNAPL chemistry analysis it was possible to correlate changes in the physical properties to depletion of alkanes from the LNAPL in a manner that would inform a quantitative NSZD assessment. LNAPL density and viscosity measurements are relatively cheap and reproducible, and increasing trends in LNAPL density and viscosity provide additional lines-of-evidence for NSZD.

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.

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.

Novel phase transfer catalysis coupled with bifunctional oxidation for enhanced remediation of groundwater polluted with multiple NAPL: Performance and mechanisms

Structural differences among non-aqueous phase liquids (NAPLs) result in varying oxidation rates, limiting mass transfer between NAPLs and oxidants and seriously impairing the effectiveness of remediation via traditional in-situ chemical oxidation. To tackle this challenge, a novel approach is proposed for remediating multi-NAPL-polluted groundwater that leverages phase transfer catalysis (PTC) to enhance heterogeneous mass transfer by transferring oxidants from groundwater to NAPLs. Meanwhile, “oxidation-in-situ activation” is achieved through bifunctional oxidation using permanganate and peroxymonosulfate (PP). The proposed approach is referred to PTC-PP in this study. Herein, trichloroethene (TCE) and benzene serve as a representative multi-NAPL system. Experimental results indicated that PP significantly improved degradation efficiency of benzene in multi-NAPL system by at least 60.8% compared to single-oxidant systems, and further enhancement (17.6%) was achieved when PP was combined with PTC compared to PP alone. Dissolved Mn(II) and MnO2 generated by MnO4− reduction effectively activated peroxymonosulfate in PTC-PP system, with colloidal MnO2 being the most effective activator. Consequently, SO4•−, O2•− and 1O2 were formed in both NAPL and aqueous phases, while •OH was formed in aqueous phase, playing a crucial role in benzene oxidation. In phase transfer process of PTC-PP, the proportion of MnO4− transferred to benzene exceeded that to TCE. This finding illustrated that nondirectional phase transfer of oxidants posed a challenge for simultaneous promotion of TCE and benzene degradation. However, TCE and benzene removal efficiencies were both >75.7% by applying peroxymonosulfate after KMnO4 addition. These findings lay the theoretical groundwork for PTC-PP application in groundwater remediation.

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.

Soil gas gradient method for estimating natural source zone depletion rates of LNAPL and specific chemicals of concern

This paper presents a simplified approach for the soil gas gradient method for estimating natural source zone depletion (NSZD) rates of specific contaminants of concern (COCs) at sites contaminated by light non-aqueous phase liquids (LNAPL). Traditional approaches to quantify COC-specific NSZD rates often rely on numerical or analytical reaction-transport models that require detailed site-specific data. In contrast, the proposed method employs simple analytical solutions, making it more accessible to practitioners. Specifically, it requires only the maximum soil gas concentration, the effective diffusion coefficient, and the diffusive reaction length calculated from vertical soil gas concentration profiles. The simplified approach was validated against a reactive transport numerical model reported in the literature, showing consistent results within the same order of magnitude for BTEX NSZD rates at a gasoline spill site in South Carolina. Further validation using a larger dataset involved comparing NSZD rate estimates for benzene and total petroleum hydrocarbons (TPH) against those obtained using BioVapor, utilizing empirical soil gas data from the USEPA Petroleum Vapor Intrusion Database. Results demonstrated a strong correlation between NSZD rates and maximum soil gas concentrations, allowing the development of a rapid screening approach based only on the measured soil gas concentrations and literature values for diffusion coefficients and diffusive reaction lengths. This approach aligned well with previous modeling studies and was consistent with literature values for TPH NSZD rates. Overall, both the simplified and screening approaches offer practical, easy-to-use tools for evaluating temporal variability in natural attenuation rates, supporting baseline assessments and ongoing performance evaluations of remediation at LNAPL sites.

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.

A New Toolbox for Managing Sites Impacted by Light Non-Aqueous Phase Liquids (LNAPLs)

The Concawe LNAPL Toolbox is one of the first completely web-based tools for managing and remediating light non-aqueous phase liquids (LNAPL) impacted sites. An off-line downloadable version is also available for users who do not want to access it via the internet. LNAPLs are typically historic hydrocarbons released into soils and groundwater, such as liquid fuels, crude oil, and condensates. The toolbox was developed by Concawe, the Scientific Division of European Fuel Manufacturers Association, with the support of the engineering and environmental science-consulting agency GSI Environmental. The toolbox, written on the R-Shiny platform, was released in 2022 and includes over 20 different tools, such as, for example, infographics, nomographs, calculators, mobility models, videos, and checklists. These tools are organized into three tiers, with Tier 1 offering basic graphics and essential information, Tier 2 providing simple quantitative models and calculators, and Tier 3 featuring access and explanations of more complex tools. The toolbox is designed to address six key questions that are important for environmental consultants and regulators managing LNAPL sites, including determining the amount of LNAPL, estimating LNAPL migration and persistence, assessing LNAPL risk over time, determining the effectiveness of LNAPL recovery, and estimating Natural Source Zone Depletion (NSZD). The Concawe LNAPL Toolbox is accessible free of charge via a webpage on an internet browser or by downloading the toolbox for use on a personal computer.

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.

Groundwater LNAPL Contamination Source Identification Based on Stacking Ensemble Surrogate Model

Groundwater LNAPL (Light Non-Aqueous Phase Liquid) contamination source identification (GLCSI) is essential for effective remediation and risk assessment. Addressing the GLCSI problem often involves numerous repetitive forward simulations, which are computationally expensive and time-consuming. Establishing a surrogate model for the simulation model is an effective way to overcome this challenge. However, how to obtain high-quality samples for training the surrogate model and which method should be used to develop the surrogate model with higher accuracy remain important questions to explore. To this end, this paper innovatively adopted the quasi-Monte Carlo (QMC) method to sample from the prior space of unknown variables. Then, this paper established a variety of individual machine learning surrogate models, respectively, and screened three with higher training accuracy among them as the base-learning models (BLMs). The Stacking ensemble framework was utilized to integrate the three BLMs to establish the ensemble surrogate model for the groundwater LNAPL multiphase flow numerical simulation model. Finally, a hypothetical case of groundwater LNAPL contamination was designed. After evaluating the accuracy of the Stacking ensemble surrogate model, the differential evolution Markov chain (DE-MC) algorithm was applied to jointly identify information on groundwater LNAPL contamination source and key hydrogeological parameters. The results of this study demonstrated the following: (1) Employing the QMC method to sample from the prior space resulted in more uniformly distributed and representative samples, which improved the quality of the training data. (2) The developed Stacking ensemble surrogate model had a higher accuracy than any individual surrogate model, with an average R2 of 0.995, and reduced the computational burden by 99.56% compared to the inversion process based on the simulation model. (3) The application of the DE-MC algorithm effectively solved the GLCSI problem, and the mean relative error of the identification results of unknown variables was less than 5%.

Imaging LNAPL distribution at a former chemical plant with time-domain induced polarization

Light non-aqueous phase liquids (LNAPLs) that infiltrate into the subsurface are commonly described in two distinct zones: the source zone and the plume zone. A precise differentiation between these zones is essential for constraining further migration and selecting an effective remediation method. In this study, we employ the induced polarization (IP) method to characterize the contaminants. Six time domain IP survey lines were conducted at a former chemical plant contaminated with LNAPLs. Even though the contaminated areas corresponding to BTEX concentration above 180 mg/kg are less than 5 mS/m, the source and plume zones cannot be distinguished by conductivity alone. However, a noticeable difference in phase (φ\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\varphi$$\\end{document}) between the two zones is observed, and the threshold phase value corresponding to a critical concentration of 450 mg/kg is 20 mrad. Moreover, the normalized chargeability (Mn\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$M_{n}$$\\end{document}) threshold for the source zone is 80 mS/m, and the corresponding Mn\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$M_{n}$$\\end{document} differences between the source and plume zones are more significant than those in φ\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\varphi$$\\end{document}. These results illustrate that changes in polarization characteristics associated with BTEX concentrations can aid in further distinguishing between the source and plume zones. Ultimately, it is concluded that IP imaging is a well-suited method for LNAPL investigations that permits an improved characterization of different contaminated zones, which can facilitate the optimization of drillings for further site assessment and remediation.

Hydrotreated vegetable oil migrates through soil and degrades faster than fossil diesel and hydrotreated vegetable oil-fossil diesel blend

HVO has been noted as a more sustainable fuel, not only leading to lower total CO2 emissions, but also resulting in lower emissions of toxic substances upon fuel burning. The environmental impact of HVO and HVO diesel blends when accidentally spilled into the soil and ground water has, however, received little attention. While HVO and diesel exhibit nearly identical viscosity and density, their behavior in soils differs due to varying water solubility and fuel additives. In laboratory- and pilot-scale soil columns and lysimeters, we compared the migration and biostimulation-enhanced degradation of HVO, HVO-diesel blend (HVO15), and fossil diesel over 120 days. Additionally, we investigated the impact of fuel additives on migration by comparing HVO without additives to HVO15 and diesel in wet and dry soil columns over 21 days. Notably, HVO migrated through soil more rapidly and in greater quantities than diesel. In wet soil, 69% of added HVO, 8.4% of HVO15, and 21% of diesel leached through as light non-aqueous phase liquid (LNAPL). Dry soil showed smaller differences in fuel migration, but HVO did not mobilize when water was added, unlike HVO15 and diesel. Biostimulation reduced HVO leaching by 15% more than HVO15 and 48% more than diesel. Overall, HVO’s behavior in soil differs significantly from fossil diesel, with factors like lower water solubility, reduced mobilization from dry soil, and higher in situ degradability contributing to its reduced environmental risk compared to fossil fuel alternatives in accident scenarios.

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.

Experimental study on migration characteristics of LNAPL in the aquitard under pumping conditions.

Research on the migration behaviors of contaminants in the aquitard has been deficient for an extended period. Clay is commonly employed as an impermeable layer or barrier to stop the migration of contaminants. However, under certain conditions, the clay layer may exhibit permeability to water, thereby allowing contaminants to infiltrate and potentially contaminate adjacent aquifers. Consequently, it holds immense importance to scrutinize and investigate the migration characteristics of light non-aqueous phase liquid (LNAPL) within the aquitard for the purposes of groundwater pollution control and remediation. To evaluate the environmental risk posed by organic contaminants in the aquitard, an experimental model was formulated and devised to monitor the LNAPL concentration in the aquitard under pumping conditions. The correlation between pumping rate and LNAPL concentration was investigated. A self-developed plexiglass sandbox model was used to simulate the migration characteristics of LNAPL in the aquitard under pumping conditions. Four experimental scenarios were designed, varying pumping rates, aquitard thicknesses, and groundwater level changes. The LNAPL concentration curve was derived by systematically tracking and analyzing LNAPL levels at various locations within the aquitard. The results indicated that higher pumping rates corresponded to increased migration of LNAPL, resulting in greater LNAPL ingress into the pumping well during extraction. A thicker aquitard demonstrated a more pronounced inhibitory effect on LNAPL, leading to an extended penetration time of LNAPL within the aquitard. The drawdown within the aquitard exerted a discernible influence on LNAPL migration, with the LNAPL concentration continuing to decrease in tandem with declining water levels during pumping. These research findings can establish a scientific foundation for the control and remediation of contaminants within aquitards.

Evaluating Natural Source Zone Depletion and Enhanced Source Zone Depletion in laboratory columns via soil redox continuous sensing and microbiome characterization

To optimally employ Natural Source Zone Depletion (NSZD) and Enhanced Source Zone Depletion (ESZD) at sites impacted by light non-aqueous phase liquids (LNAPL), monitoring strategies are required. Emerging use of subsurface oxidation-reduction potential (ORP) sensors shows promise for tracking redox evolution, which reflects ongoing biogeochemical processes. However, further understanding of how soil redox dynamics relate to subsurface microbial activity and LNAPL degradation pathways is needed. In this work, soil ORP sensors and DNA and RNA sequencing-based microbiome analysis were combined to elucidate NSZD and ESZD (biostimulation via periodic sulfate addition and biosparging) processes in columns containing LNAPL-impacted soils from a former petroleum refinery. Results show expected relationships between continuous soil redox and active microbial communities. Continuous data revealed spatial and temporal detail that informed interpretation of the hydrocarbon biodegradation data. Redox increases were transient for sulfate addition, and sequencing revealed how hydrocarbon concentration and composition impacted microbiome structure and naphthalene degradation. Periodic biosparging did not result in fully aerobic conditions suggesting observed biodegradation improvements could be explained by alternative anaerobic metabolisms (e.g., iron reduction due to air oxidizing reduced iron). Collectively, data suggest combining continuous redox sensing with microbiome analysis provides insights beyond those possible with either monitoring tool alone.

Numerical simulation and experimental study of three-phase distribution characteristics of leaked light non-aqueous phase liquid from buried pipelines in soils containing groundwater and gas.

Leakage accidents of buried pipelines have become increasingly common due to the prolonged service of some pipelines which have been in use for more than 150years. Therefore, there is an urgent need for accurate prediction of pollution scope to aid in the development of emergency remediation strategies. This study investigated the distribution of a light non-aqueous phase liquid in soils containing gas and water through numerical simulations and laboratory experiments. Firstly, a three-dimensional porous medium model was established using ANSYS FLUENT, and for the first time, the distribution of gas and groundwater in soil environments was simulated in the model. Subsequently, the distribution of the three phases of diesel, gas, and water in soil was studied with different leakage velocities and it was found that the leakage velocity played a significant role in the distribution. The areas of diesel in soils at 60min were 0.112m2, 0.194m2, 0.217m2, and 0.252m2, with corresponding volumes of 0.028m3, 0.070m3, 0.086m3, and 0.106m3, respectively, for leakage velocities of 1.3m/s, 3.4m/s, 4.6m/s, and 4.9m/s. Calculation formulas for distribution areas and volumes were also developed to aid in future prevention and control strategies under different leakage velocities. The study also compared the distribution areas and volumes of diesel in soils with and without groundwater, and it was found that distribution scopes were larger in soils containing groundwater due to capillary force. In order to validate the accuracy of the numerical simulation, laboratory experiments were conducted to study the diffusion of oil, gas, and water under different leakage velocities. The results showed good agreement between the experiments and the simulations. The research findings are of great significance for preventing soil pollution and provide a theoretical basis for developing scientifically sound soil remediation strategies.

Impacts of LNAPL types on mechanisms and rate of natural source zone depletion

Understanding the mechanisms of natural source zone depletion (NSZD) will support an improved understanding of the long-term sustainability of NSZD as a site remedy and how NSZD rates may change over time. This is the first study that has quantified and compared the rate of three NSZD mechanisms (methanogenesis, vaporization, and aqueous biodegradation) between two chemically distinct light non-aqueous phase liquid (LNAPL) source zones (aliphatic-rich naphtha for Zone #1 vs aromatic-rich pyrolysis gasoline for Zone #2) within the same geologic and climate conditions. The rates of NSZD attributable to vaporization (400 mg C/m2/d vs. 300 mg C/m2/d) and aqueous biodegradation (92 mg C/m2/d vs. 67 mg C/m2/d) were similar for Zone #1 and #2; however, the rate of methanogenesis NSZD was 6x higher in Zone #1 (1000 mg C/m2/d vs. 170 mg C/m2/d). These results suggest that the aliphatic hydrocarbons content in an LNAPL source may be a factor in the rate of methanogenesis NSZD. For both Zone #1 and #2, total NSZD rate determined using this “three mechanism” measurement method was in reasonable agreement with two other methods used to measure total NSZD rates (CO2 Gradient Method and Dynamic Closed Chamber Method), validating the “three mechanism” method as a tool to measure the total NSZD rate at a site and to provide an improved understanding of the predominant NSZD mechanism. Overall, this study highlights the importance of LNAPL type and chemical characteristics in determining source zone natural attenuation mechanism and its total rates.

Unravelling the influence of heterogeneities and abstraction on groundwater flow and solute transport in a fractured carbonate aquifer, Sicily, Italy

The migration of a groundwater contaminant plume consisting of light nonaqueous phase liquids (LNAPLs) along the Ionian coastline of Sicily, Italy, has been reported to follow a trajectory that is inconsistent with the regional hydraulic gradient. The influence of several faults affecting the fractured carbonate bedrock aquifer, and groundwater abstraction from a well, were hypothesized to be responsible for the anomalous trajectory of the contaminant plume. A conceptual hydrogeological model was developed for the study area that incorporated structural information derived from geophysical surveys and the mapping of fractures in bedrock outcrops. This conceptual model was incorporated into numerical groundwater flow and solute transport models to simulate the groundwater transport of the light nonaqueous phase liquids. Four model scenarios representing different levels of complexity were tested to assess the relative influence of geological heterogeneity and groundwater abstraction on the migration of the contaminant plume. Results show that underground major discontinuity systems, invoking the presence of the faults in the model domain accounted for the observed migration of the contaminant plume, act as conduits for groundwater flow. Conversely, groundwater abstraction from a well was found to result in relatively minor, localized impacts to the migration of the contamination plume. This study demonstrates the importance of incorporating geological heterogeneity into groundwater modelling and environmental risk assessments associated with the storage of LNAPLs.