LNAPL Research Articles

Multimethod Analysis of NSZD and Enhanced SZD by Solar‐Powered Bioventing at the Guadalupe Restoration Project

AbstractActive remediation at sites with light non‐aqueous phase liquid (LNAPL) often leaves residual hydrocarbons in the subsurface, necessitating long‐term management. While much of the effort in recent years has focused on natural source zone depletion (NSZD) as the primary method for demonstrating continued hydrocarbon removal, the same data collection methods can quantify biodegradation enhancements that can sustainably increase the rate of SZD. This approach has been applied at the Guadalupe Restoration Project, one of the first sites at which NSZD measurements and monitoring technology were demonstrated. Sitewide NSZD quantification was conducted using CO2 efflux measurements and subsurface temperature profiling. The results fell within the range of previously reported estimates that were based on soil‐gas profiling in the early 2000s, demonstrating the viability of the new methods at this site. The data collection methods were then deployed during pilot testing of solar‐powered bioventing. The system used seven 400‐W solar panels to power a regenerative blower that delivered approximately 0.85 cubic meter per minute (30 cfm) air to the LNAPL‐impacted vadose soil near the interface with the groundwater table. Soil‐gas data indicated an upward fanning of injected air toward ground surface. Elevated temperature due to hydrocarbon oxidation yielded an approximate 10.2 kg day−1 source depletion rate above the baseline NSZD mass removal rate over an approximate 30 m (100 ft) radius of influence, which aligned well with a 8.2 kg day−1 rate estimated from CO2 efflux measurements. Introduction of O2 via bioventing substantially increased the LNAPL biodegradation rate from baseline NSZD processes by almost an order of magnitude. The results demonstrate that site management can proceed along a sequenced program that began with aggressive hydraulic recovery of hydrocarbon product, transitions to enhanced SZD in areas with poorly recoverable LNAPL, and then to NSZD without intervention to address residual LNAPL across the full footprint of the LNAPL bodies.

Evaluation of factors causing lateral migration of light non-aqueous phase liquids (LNAPLs) in onshore oil spill accidents.

Contamination of groundwater by harmful substances poses significant risks to both drinking water sources and aquatic ecosystems, making it a critical environmental concern. Most on-land spill events release organic molecules known as light non-aqueous phase liquids (LNAPLs), which then seep into the ground. Due to their low density and organic composition, they tend to float as they reach the water table. LNAPLs encompass a wide range of non-aqueous phase liquids, including various petroleum products, and can, over time, develop carcinogenic chemicals in water. However, due to frequent changes in hydraulic head, the confinement may fail to contain them, causing them to extend outward. When it contaminates water wells, people cannot reliably consume the water. The removal of dangerous contaminants from groundwater aquifers is made more challenging by LNAPLs. It is imperative to analyze the mechanisms governing LNAPL migration. As a response to this need and the associated dispersion of contaminants into adjacent aquifers, we have conducted a comprehensive qualitative literature review encompassing the years 2000-2022. Groundwater variability, soil structure, and precipitation have been identified as the three primary influential factors, ranked in the following order of significance. The rate of migration is shown to rise dramatically in response to changes in groundwater levels. Different saturation zones and confinement have a major effect on the lateral migration velocity. When the various saturation zones reach a balance, LNAPLs will stop moving. Although higher confinement slows the rate of lateral migration, it speeds up vertical migration. Beyond this, the lateral or vertical movement is also influenced by differences in the permeability of soil strata. Reduced mobility and tighter containment are the outcomes of migrating through fine-grained, low-porosity sand. The gaseous and liquid phases of LNAPLs move more quickly through coarse-grained soils. Due to the complexities and uncertainties associated with LNAPL behavior, accurately foreseeing the future spread of LNAPLs can be challenging. Although studies have utilized modeling techniques to simulate and predict LNAPL migration, the inherent complexities and uncertainties in the subsurface environment make it difficult to precisely predict the extent of LNAPL spread in the future. The granular soil structure considerably affects the porosity and pore pressure.

Past, Present, and Future Anatomy of an Oil Brine Plume Remediation near Poplar, Montana: A Case Study

AbstractThe Biere #1‐22 oil production well near Poplar, Montana leaked brine and light nonaqueous phase liquid (LNAPL) to the shallow alluvial aquifer for several years before final closure in 2002. Since 2008, 2.5 billion L of brine have been removed (~90% of the original Cl mass). However, Cl will not reach the original background levels due to the reservoir of solutes entrained in the Bearpaw bedrock remnant from the lateral dense aqueous phase liquid flow across the alluvial/bedrock interface. After removal of ~100,000 L of product since 2006, residual LNAPL is now confined to 2.2 ha (5.5 acres) a decrease from the original 2.7 ha (6.6 acres) areal extent by 17%. The initial ~7.5 m thick product in 2002 is stable at a maximum of ~1 m. However, LNAPL has infiltrated into fine‐grained clay/silt units forming a smear zone in lenses 10 to 20 m bgs. Ongoing remediation has successfully mitigated benzene groundwater impacts over the last 14 years, with the benzene plume area having decreased by >99% (at the 5 μg/L) level from the maximum ~140 ha in 2002. This appears to be the first study evaluating the challenges to remediate a mixed LNAPL/dissolved organic/inorganic plume. Based on the mass removal to date, the asymptotic trends in solute concentrations, unpotable background groundwater quality, absence of a source/receptor pathway, lack of beneficial groundwater use, duration of mitigation with no obvious future accrual in benefit and the availability of institutional controls, it seems that the remedial strategies employed since 2006 have met their cost/benefit goals.

Understanding petroleum vapor fate and transport through high resolution analysis of two distinct vapor plumes

No field study has provided a detailed characterization of the molecular composition and spatial distribution of a vadose zone plume of petroleum volatile organic compounds (VOCs), which is critical to improve the current understanding of petroleum VOC transport and fate. This is study reports a high-resolution analysis of two distinct vapor plumes emanating from two different light non-aqueous phase liquid (LNAPL) sources (an aliphatic-rich LNAPL for Zone #1vs an aromatic-rich LNAPL for Zone #2) at a large petrochemical site. Although deep soil vapor signatures were similar to the source zone LNAPL signatures, the composition of the shallow soil vapors reflected preferential attenuation of certain hydrocarbons over others during upward transport in the vadose zone. Between deeper and shallower soil gas samples, attenuation of aromatics was observed under all conditions, but important differences were observed in attenuation to aliphatic compound classes. Attenuation of all aliphatic compounds was observed under aerobic conditions but little attenuation of any aliphatics was observed under anoxic conditions without methane. In contrast, under methanogenic conditions, paraffins attenuated more than isoparaffins and naphthenes. These results suggest that isoparafins and naphthenes may present more of a vapor intrusion risk than benzene or other aromatic hydrocarbons commonly considered to be petroleum vapor intrusion risk drivers. While the overall vapor composition changed significantly within the vadose zone, diagnostic ratios of relatively recalcitrant alkylcyclopentanes were preserved in shallow soil vapor samples. These alkylcyclopentanes may be useful for distinguishing between petroleum vapor intrusion and other sources of petroleum VOCs detected in indoor air.

Partitioning of Per‐ and Polyfluoroalkyl Substances to Weathered Light Non‐Aqueous Phase Liquid

AbstractPer‐ and polyfluoroalkyl substances (PFAS) and weathered petroleum hydrocarbons can be co‐contaminants at sites where aqueous film‐forming foam (AFFF) was used to extinguish high‐temperature petroleum fires. Here, we report on the partitioning of six PFAS between water and a weathered diesel and gasoline range hydrocarbon light non‐aqueous phase liquid (LNAPL) collected from the subsurface of a decommissioned refinery. Results showed that both the structural features of PFAS and the characteristics of LNAPL exhibited significant impacts on the magnitude of PFAS partitioned to the LNAPL. The LNAPL–water partition coefficients (Kl) of PFOA and PFOS to the weathered LNAPL measured in this work were nearly or more than 10 times greater than Kl values calculated by others for partitioning to single‐component, unweathered NAPLs, indicating that laboratory studies evaluating LNAPL–water partitioning studies using single component NAPLs can largely underestimate the Kl expected to be encountered at contaminated AFFF sites. Interactions with LNAPL can be important controllers of PFAS fate and transport, and the Kl values estimated in this work suggest that LNAPL could be a significant transport sink for PFAS in the field. Results from this work suggest that PFAS partitioning to weathered LNAPL is an important process to be considered when designing remedial strategies, particularly those incorporating monitored natural attenuation or natural source zone depletion.

Vertical Light Non-Aqueous Phase Liquid (LNAPL) distribution by Rn prospecting in monitoring wells.

In the frame of a collaboration between the Italian National Research Council (CNR) and Mares s.r.l., a study, about the possibility of determining radon vertical distribution at different soil depths in order to trace light non-aqueous phase liquid (LNAPL) contaminations, was developed. The radon deficit technique, based on the preferential solubility of soil gas radon into non-polar fluids, such as refined hydrocarbons, has been investigated by various theoretical and applied research so far. According to international scientific literature, radon deficit can be used both for geochemical prospection of the spatial irregular NAPL dispersion and for monitoring of remediation activities. Even though it is well known that this type of pollutants can be distributed along the vertical soil profile-firstly due to their density in comparison to water density, and secondly due to fluctuations of shallow aquifers, soil pore size, aging of contamination, and so on-the vertical localization of the plume still represents a scientific challenge. In this article, a method to determine the radon vertical profile is tested and applied to assess the potential use of the radon deficit technique in the vertical detection of pollutant presence for the first time in a fuelling station. Two LNAPL-contaminated sites were selected for a pilot test. Experimental findings seem to support the use of vertical radon geochemical prospection to delimit the depth range of a LNAPL pollution directly. Systematic data collection and modeling may lead to a 3D reconstruction of the dispersion of contaminant in different soil levels.

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

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

LNAPL migration processes based on time-lapse electrical resistivity tomography

Contamination from light non-aqueous phase liquids (LNAPLs) and their derivatives, arising from exploration, production, and transportation, has become a prevalent pollution source. This poses direct threats to human health. However, conventional investigative methods face limitations when applied to studying the extent and migration process of LNAPL contamination, as well as the redistribution of LNAPL during groundwater level fluctuations. Conventional methods lack the ability to rapidly, efficiently, and in real-time acquire information about contaminated areas. Therefore, this study utilizes time-lapse electrical resistivity tomography to investigate the migration mechanism of LNAPL under unsaturated conditions, constant groundwater levels, and groundwater level reductions. A relationship between resistivity and water and oil contents was established and used for inverse calculation of LNAPL content via resistivity inversion. Time-lapse electrical resistivity tomography revealed LNAPL migration in a “concave” shape across three conditions. Groundwater presence notably slowed migration, hindering downward movement and leading to a floating oil band. A robust mathematical model was established to derive the relationship between resistivity and water and oil contents. Finally, LNAPL distribution under unsaturated conditions was inversely obtained from resistivity data, showing highest content at the top leak point, obstructed area, and bottom of soil column. Consequently, time-lapse electrical resistivity tomography demonstrates a notable capacity to characterize the LNAPL migration process. This technique constitutes an effective geophysical method for monitoring and describing the characteristics of LNAPL migration. Its significance lies in enhancing our understanding of remediation for LNAPL-induced groundwater and land contamination.

Fabrication of plasma-treated superhydrophobic polydimethylsiloxane (PDMS) – Coatėd melamine sponge for enhanced adhesion capability and sustainable oil/water separation

A persistent global issue is the need for developing novel absorbent materials with high absorption efficacy and rapid absorption rates for effective oil–water separation. This work presents a novel, resilient, and recyclable material with exceptional sorption capabilities, achieved through a simple surface modification of melamine sponge (MS) using Argon plasma treatment followed by Polydimethylsiloxane (PDMS) polymer coating (Ar-PT/PDMS@MS). This study also delineates the choiceful impact of atmospheric and vacuum plasma over the surface modification of MS. The material's super hydrophobicity, demonstrated by a high-water contact angle of ∼165°, is enhanced using novel plasma treatment to homogenously coat PDMS polymer. This treatment also imparts sturdiness to withstand harsh environmental conditions. The modified 3D networked structure of melamine sponge with a porous core was able to selectively absorb the oil of various densities with the capacity range of 42–139.5 mg/g. The batch and continuous O/W separation studies revealed the efficiency of the modified MS to be able to selectively separate light nonaqueous phase liquids (LNAPL) and dense nonaqueous phase liquids (DNAPL) oil with more than 99% efficiency. The continuous studies showed that using diesel oil the separation efficiency was >99% for 35 L of oil for more than 5 h. It was also discovered that it outperformed and exceeded commercial absorbent materials in terms of absorption capacity. The recyclability studies highlighted the ability of the modified MS to be used for more than 10 cycles without compromising its separation efficiency. These findings may foreshadow Ar-PT/PDMS@MS's ability to be a promising antagonist for oil–water (O/W) separation in real-world oil-spill scenarios.

Radiometric dating of Light Non-Aqueous Phase Liquids (LNAPLs) dispersed in soil: A low environmental impact tool for natural resource restorations and protection

Non-polar liquids released in environment cause a long-term soil and groundwater contamination. The costs associated with a multi-year remediation are high and the uncertainty in the allotment of legal responsibilities could defer the decontamination planning. Therefore, a reliable method to assess the residence time of spilled Non-Aqueous Phase Liquids (NAPLs) in soil is highly needed. In this paper, a method, using low environmental radioactivity and radiometric dating, is described and applied to real contaminations. After being alpha-recoiled from 232Th in soils,228Ra accumulates in light NAPLs, generating 228Th. A disequilibrium clock, based on γ-spectrometric determination of the ratio 228Th/228Ra, was conceived to measure the residence time of LNAPL pollutants in a soil. The pollutant extraction and γ-counting procedures are described. This approach inverts the role played by pollutants and contaminated matrixes, because the flux of alpha recoil from soil generates in pollutants a reliable model of “closed system”, which is preserved in LNAPLs due to the peculiar properties of non-polar liquids. All case studies are sited in Italy and have been supported by preliminary lab tests. Dating tests of 15 samples (including LNAPLs, contaminated soils and oil socks) were performed, in most cases, blindly. Then, the results were compared to historical data about contaminations. A good correlation between test results and site history was generally obtained. But an increasing error has to be considered in old contaminations due to the nonlinear nature of disequilibrium time equation. Other reasons of discrepancies, due to system opening, include the use of surfactants, the presence of significant amount of MnO2 in soil and the interactions of different spillages. The outcomes of this research evidence the possibility to precisely date the contamination both in soil and in non-polar liquids, offering a potential tool to settle legal disputes. Further studies could broad and improve the applicability of the method.

On quantifying global carbon emission from oil contaminated lands over centuries

Petroleum releases into the subsurface contribute to global soil carbon emissions. Quantifying releases and changes in releases of carbon from soils over the lifetime of a spill is complex. Natural source zone depletion (NSZD) of light non-aqueous phase liquids (LNAPLs) embodies all key mechanisms for transformation to carbon gases and their release from soils including partitioning, transport and degradation of petroleum components. Quantification of the interconnected behaviours of the soil microbiome, fluid flow, multi-component transport, partitioning, and biodegradation is crucial for understanding NSZD. Volatilization from LNAPL, aerobic biodegradation, methanogenesis, and heat production all lead to release of greenhouse gases to the atmosphere. To estimate carbon emissions, using a validated computational platform, we modelled the long term NSZD of four petroleum hydrocarbon types; crude oil, diesel, jet fuel and gasoline, to span the major products used globally. For two soil types, we estimated 150 years of carbon emissions from annual minor and 25 mostly major petroleum hydrocarbon land release incidents since 1950 – with an estimated released mass of ~9 million tonnes across the circumstances considered. Up to 2100 the mass of carbon emitted to the atmosphere is estimated to range from 4 to 6 Teragrams, with nearly 60 % currently released. Nomographs generated help predict the fate of LNAPL plumes and carbon emissions due to NSZD, which is crucially important to management of soil and groundwater contamination. The method provides a basis to include additionally identified and future petroleum releases. It is noted that the petroleum mixture composition, degradation rates, volatilization, and subsurface characteristics all can influence carbon emission estimations.

Development and Application of an Integrated Site Remediation Technology Mix Method Based on Site Contaminant Distribution Characteristics

Millions of contaminated sites worldwide need to be remediated to protect the environment and human health. Although numerous remediation technologies have been developed, selecting optimal technologies is challenging. Several multiple criteria decision-making methods for screening the optimal remediation technology have been proposed, but they mostly focus on a specific area rather than the whole contaminated site. In recent years, the “contamination source control—process blocking—in situ remediation” technology mix model has gradually gained high appreciation. Nevertheless, the screening of technologies within each chain of this model relies heavily on arbitrary personal experience. To avoid such arbitrariness, a petroleum-contaminated site containing light non-aqueous phase liquids (LNAPLs) was used as an example, and a scientific screening and combination procedure was developed in this study by considering the distribution characteristics of contaminants. Through the procedure, a technology mix, which includes institutional control, risk monitoring, emergency response, multiphase extraction, interception ditch, monitoring of natural attenuation, hydrodynamic control, as well as some alternative technologies, was found, aiming at different locations and strata. The clear spatial relationship concept promises to enhance the effectiveness of contaminated site remediation. The proposed method only gave us a technical framework and should be tested and enriched in future studies.

Phase behavior of sulfolane: Potential implications for transport in groundwater

Sulfolane is a toxic pollutant freely miscible in pure water. However, above benchmark concentrations of sulfate or thiosulfate ions, it behaves as a light non-aqueous phase liquid and separates into either bulk phases or kinetically stable emulsions. Sulfolane droplets bear a negative electrostatic charge, as revealed by electrophoretic measurements. With high sulfate salt concentrations, the counterions screen the negative charge of sulfolane droplets. This promotes droplet coalescence and bulk phase separation, as well as droplet adhesion onto negatively charged mineral substrates such as clay and sand. NaCl does not separate sulfolane from water but favors its partitioning into toluene, as demonstrated by attenuated total reflectance-Fourier transform infrared spectroscopy. Water activity measurements show that sodium sulfate interacts with water more strongly than sulfolane, justifying its ability to displace sulfolane and induce its separation. Both sulfolane and sulfate ions interact with water through hydrogen (H) bonds. Water is comprised of water species that donate and accept a different number of H bonds, depending on other molecules in water. Sulfolane is an H bond acceptor. Therefore, it mainly interacts with double H bond donors that either do not accept H or accept only one H (double donor-single acceptor, DD-SA). ATR-FTIR data indicate that sulfate ions compete with sulfolane more effectively than chlorides for interactions with DD-SA, thereby promoting better separation. Sulfolane phase separation can retard its migration in polluted aquifers. This study reveals the complex behaviour of sulfolane in water, with potential implications for sulfolane transport in groundwater.

Using groundwater monitoring wells for rapid application of soil gas radon deficit technique to evaluate residual LNAPL

The application of the 222Radon (Rn) deficit technique using subsurface soil gas probes for the identification and quantification of light non-aqueous phase liquids (LNAPL) has provided positive outcomes in recent years. This study presents an alternative method for applying this technique in the headspace of groundwater monitoring wells. The developed protocol, designed for groundwater monitoring wells with a portion of their screen in the vadose zone, is based on the use of portable equipment that allows rapid measurement of the Rn soil gas activity in the vadose zone close to the water table (i.e., smear zone) where LNAPL is typically expected. The paper first describes the step-by-step procedure to be followed for the application of this method. Then, a preliminary assessment of the potential of the method was carried out at two Italian sites characterized by accidental gasoline and diesel spills into the subsurface from underground storage tanks. Although the number of tests conducted does not allow for definitive conclusions, the results obtained suggest that, from a qualitative point of view, Rn monitoring in the headspace of monitoring wells is a promising, fast, and minimally invasive screening method that could also potentially reduce the costs associated with field data acquisition. This method proves to be suitable for detecting the presence of LNAPL in both the mobile and residual phases with results consistent with the other lines of evidence available at the sites, such as groundwater and soil gas monitoring. Future efforts should be directed toward evaluating the accuracy of this method for a quantitative assessment of residual LNAPL saturations.

The impact of water table fluctuation and salinity on LNAPL distribution and geochemical properties in the smear zone under completely anaerobic conditions

Climate and groundwater are always in a state of dynamic equilibrium. Subsurface systems contaminated by light non-aqueous phase liquid (LNAPL) present a challenge to understand the overall impact of water table dynamics, due to various interacting mechanisms, including volatilization, and LNAPL mobilization/dissolution along the groundwater flow direction and oscillating redox conditions. We investigated the impact of water table fluctuations on LNAPL natural attenuation and soil geochemical characteristics in semi-arid coastal areas under saline conditions. Four soil columns operated for 151 days under anoxic conditions where a layer of benzene and toluene were subjected to a stable and fluctuating water table associated with low and high salinity conditions. The bottom of stable and fluctuating columns reached an anaerobic state after 40 days, while the middle of stable column took 60 days. pH values of the fluctuating columns covered a wide range, and at the end shifted towards alkaline conditions, unlike the stable columns. In fluctuating columns, pore water sulfate decreased in the middle, but in stable columns, it decreased in the first 40 days, which suggested that sulfate was the primary electron donor and sulfate-reducing bacteria were present. At the source zone, benzene and toluene reached their maximum concentration after 30 and 10 days for the stable and the fluctuating columns, respectively. Significant decrease in benzene and toluene concentrations occurred under the fluctuating water table. Salinity did not affect benzene and toluene concentrations in the aqueous phase, although water table fluctuations have the most effect. Soil solid-phase analysis shows fluctuating columns have less toluene than stable columns. Solid-phase analysis showed the fluctuating columns have less benzene and toluene concentrations as compared to the stable columns.

The Migration Mechanism of BTEX in Single- and Double-Lithology Soil Columns under Groundwater Table Fluctuation.

The migration of light non-aqueous phase liquids (LNAPLs) trapped in porous media is a complex phenomenon. Groundwater table fluctuation can not only affect contaminant migration but also redox conditions, bacterial communities, and contaminant degradation. Understanding LNAPLs' (e.g., benzene, toluene, ethylbenzene, and xylene (BTEX)) behavior within porous media is critical for the high efficiency of most in situ remediation systems. A laboratory study of single- and double-lithology soil column investigation of the groundwater table fluctuation effect on BTEX transport, using benzene and toluene as typical compounds, in a typical representative model of aquifers subjected to water table fluctuation was undertaken in this study. The results show that benzene and toluene migration in single-lithology soil columns packed with sand was mainly affected by flushing due to the hydraulic force induced by water table fluctuations and that the double-lithology soil column packed with sand and silt was significantly affected by retention due to the higher adsorption induced by 10 cm of silt. The dissolution mainly correlated with the BTEX migration in saturated zones, and the contaminant concentration increased when the water table fell and decreased when the water table rose. For a contaminated site with a single-lithology structure consisting of sand, more attention should be paid to organic contaminant removal within the groundwater, and a double-lithology structure containing silt is more suited to the removal of organic contaminants from the silt layer. The difference in biodegradation kinetics between the groundwater table fluctuation (GTF) zone and the saturated zone should be better understood for the remediation of BTEX compounds.

Transition from active remediation to natural source zone depletion (NSZD) at a LNAPL-impacted site, supported by sustainable remediation appraisal

Natural source zone depletion (NSZD) is increasingly being considered as a risk-management option at sites impacted with light non-aqueous phase liquids (LNAPLs). NSZD can be applied in isolation or in combination with active remediation techniques, depending on site-specific risk-management requirements. A case study of the transition from active remediation to passive NSZD is presented for a petroleum-impacted site in NW Europe. This transition was supported by multiple lines of evidence/management options, including: the introduction of institutional controls on groundwater and land-development restrictions; the results from a residual-NAPL risk assessment; monitoring to establish that the LNAPL plume is reducing in size; a LNAPL transmissivity assessment; a CO 2 equivalent assessment of remediation options; and a LNAPL recovery diminishing returns model. Through application of local sustainable remediation principles consistent with ISO/SuRF-UK sustainable remediation frameworks and tools, regulatory approval was obtained for a partial closeout of the remediation system. By the final year of operation, NSZD rates in the portion of the site on which transition to NSZD has been agreed were over three times greater than active LNAPL recovery rates (12 000 l/ha/a for NSZD; 3800 l/ha/a for active LNAPL recovery). In the remaining active remediation areas total fluids extraction currently outperforms NSZD and will be continued until a comparable point is reached when NSZD removal exceeds active remediation. At that point transition to NSZD alone will be considered as the most sustainable risk-based approach.

Update to the light nonaqueous phase liquid infiltration conceptual model

AbstractThe 1970s oil spill model described the infiltration of oil (light nonaqueous phase liquid or LNAPL) into the subsurface, resulting in an oil pancake depressing the water table within the capillary fringe. An update to the 1970s model is needed because, according to the discussion by Lenhard et al. on the work of Lenhard and Parker and Farr et al., “A key concept of their efforts was that LNAPL‐saturated ‘pancakes’ do not exist.” Lenhard and Parker and Farr et al. showed that the distribution of water, LNAPL, and air in the subsurface was a function of the LNAPL, water, and air pressures; fluid properties; and the pore‐size distribution of the porous medium, and that the fluid saturations can be calculated from fluid levels in a monitoring well. The 1970s oil spill infiltration model described that spilled LNAPL migrates downward through the vadose zone under the force of gravity with some lateral spreading. The vadose zone, where all of the liquid pressures are less than atmospheric pressure, becomes a three‐fluid zone consisting of variable saturations of air, water, and LNAPL, which together fully saturate the pore spaces. One important update to the 1970s model is that instead of the infiltrating LNAPL stopping at and depressing the water table, LNAPL penetrates the water table to a depth consistent with the gravitational and capillary forces experienced during LNAPL infiltration and creates a two‐fluid zone below the water table where LNAPL and water pressures are greater than atmospheric pressure. After the LNAPL release stops, LNAPL infiltration and migration will cease after reaching equilibrium. The updated LNAPL infiltration conceptual model, like the 1970s model, describes the situation where the LNAPL release has stopped and LNAPL infiltration and migration have ceased after reaching equilibrium. The volume of LNAPL released is also assumed to be sufficient to pass through the vadose zone and enter the saturated zone.

Influence of porosity and temperature on light non-aqueous phase liquid diffusion in soils

Soil characteristics play an important role in distribution of light non-aqueous phase liquid (LNAPL) spilled from buried pipeline, and enhanced understanding of distribution is significant to the effective design of soil and groundwater remediation strategies. Therefore, distribution of diesel in soils with different porosity and temperature on the temporal evolution of the diesel migration following the saturation profiles of the two-phase flow in soils were investigated in this study. The diffusion ranges, areas and volumes in both the radial as well as in axial directions of leaked diesel in soils with different porosity and temperature increased with time. Soil porosities played an important role in the distributions when soil temperatures had no effect on distributions of diesel in soils. The distribution areas were 0.385 m2, 0.294 m2, 0.213 m2, and 0.170 m2 at 60 min when the soils porosities were 0.1, 0.2, 0.3, and 0.4, respectively. The distribution volumes were 0.177 m3, 0.125 m3, 0.082 m3, 0.060 m3 at 60 min when the soils porosities were 0.1, 0.2, 0.3, and 0.4, respectively. But the distribution areas were 0.213 m2 at 60 min when the soil temperatures were 286.15 K, 296.15 K, 306.15 K and 316.15 K, respectively. The distribution volumes were 0.082 m3 at 60 min when the soil temperatures were 286.15 K, 296.15 K, 306.15 K and 316.15 K, respectively. The calculation formulas of distribution areas and volumes of diesel in soils with different porosity and temperature for developing prevention and control strategies in the future were fitted. The seepage velocities of diesel changed sharply around the leakage port and decreased from about 4.9 m/s to 0 within a few millimeters in soils with different porosity. Additionally, the diffusion ranges of leaked diesel in soils with different porosity were different, indicating that soil porosity had a significant impact on seepage velocities and pressures. The seepage velocities fields and pressures fields of diesel in soils with different temperature were same at the leakage velocity of 4.9 m/s. And the study could provide some supports for determination of the safety zone and formulation of emergency response plans for LNAPL leakage accidents.

The effects of water table fluctuation on LNAPL deposit in highly permeable porous media: A coupled numerical and experimental study

Light Non-Aqueous Phase Liquid (LNAPL) flow on the water table is highly mobile and is sensitive to the fluctuation of groundwater. This process is highly complex and involves the migration of three immiscible phases (i.e. water, LNAPL and air) which need the explicit definition of multiple parameters. A coupled experimental and numerical simulation methodology is performed by using Time Domain Reflectrometer (TDR) and multiphase simulation of a controlled environment to mimic the water table fluctuation and its effect on the LNAPL residual saturation. TDR probes are installed in different locations of a 2D tank (i.e. a cuboid box with relatively low off-plane thickness) and the bulk permittivity of the phases are measured through artificially imposed boundary conditions. The bulk permittivity is then translated into saturation of the three different phases. The translated residual saturations along with the previously measured porous media properties (e.g. porosity and saturated permeability) are then inserted into the numerical simulator (i.e. COMSOL Multiphysics®) and the migration of the three phase in porous media is simulated. The numerical exponents and entry pressures needed for the simulation of the multiphase flow are estimated using the temporal experimental values. The exponents of water LNAPL relative permeability were estimated to be around 2 while the exponents gas LNAPL relative permeability were estimated to be closer to 3. The results, simulated with the optimized parameters, are then evaluated with pictures taken from the transparent face of the 2D tank different stages of the experiment. The temporal evolution of different phase saturation has been compared and validated between the experimental results obtained and interpreted by the TDR probe measurements and the simulations. The relative error stays in the 5 % confidence level for most reported points and only in the highly dynamic flow time steps the error reaches around 12% which are discussed in the text and is accepted due to the highly nonlinear nature of the problem.