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 150 years. 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 60 min were 0.112 m2, 0.194 m2, 0.217 m2, and 0.252 m2, with corresponding volumes of 0.028 m3, 0.070 m3, 0.086 m3, and 0.106 m3, respectively, for leakage velocities of 1.3 m/s, 3.4 m/s, 4.6 m/s, and 4.9 m/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.

Retention effect and mode of capillary zone on the migration process of LNAPL pollutants based on experimental exploration.

Two-dimensional sand tank experiments were designed to investigate the retention process of the capillary zone during the migration of light non-aqueous phase liquid (LNAPL) pollutants. The fine sand and silt media experiments simulated the LNAPL migration process given a shallow point source leakage scenario. The results indicate that the LNAPL was retained in the capillary zone. A retention factor, based on the ratio of the change in the vertical migration velocity of the LNAPL front with time, was proposed to quantitatively characterize the retention effect. The retention factor and time satisfied the function of σ=A×exp(-kt). And the retention factor increased gradually with time, indicating the enhanced retention effect of capillary zone on the vertical migration of LNAPL. The concentration change rate was then used to investigate the LANPL redistribution process, which had a relationship with time of νc=B×ln(t)+C. The capillary zone could be divided from top to bottom into a weak retention zone (B > 0, vc < 0), a strong retention zone (B < 0), and a barrier zone (B > 0, vc > 0). The retention effect of capillary zone on LNAPL migration gradually strengthened during the vertical migration of LNAPL. In addition, the coefficient B had a relationship with the environmental factors (i.e., EC, pH, and ORP) of B=a×sin(b×α×ß×γ)c and the fitting coefficient R2 of the function was above 0.913 for both media, indicating a strong correlation between the LNAPL redistribution process and the key environmental factors.

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.

Optimization of Dominant Frequency and Bandwidth Analysis in Multi-Frequency 3D GPR Signals to Identify Contaminated Areas.

Ground-penetrating radar (GPR) has been widely used in investigations of contaminated areas because of its sensitivity to variations associated with the nature of pore fluids. However, most of the studies were usually based on the visual interpretation of radargrams or on a time domain amplitude analysis. In this work, we propose a methodology that consists of analyzing the spectral content of the signal recorded in multi-frequency 3D GPR profiles. A remarkable advantage of this type of antenna is its step-frequency system, which provides a much wider emission spectrum than the one corresponding to conventional single-frequency antennas. From the data in the frequency domain, the dominant frequency and bandwidth were calculated as parameters whose variation could be related to the presence of light non-aqueous phase liquid (LNAPL) in the subsurface. By analyzing the variations of these two parameters simultaneously, we were able to delimit the contaminated zones in a case study, associating them with a significant shift of the frequency spectrum with respect to the average of the study area. Finally, as a validation method of the proposed methodology, the results of the frequency analysis were compared with resistivity data obtained with an electromagnetic conductivity meter, showing a very good correlation between the results.

Quantifying the benefits of in-time and in-place responses to remediate acute LNAPL release incidents.

Acute large volume spills from storage tanks of petroleum hydrocarbons as light non aqueous phase liquids (LNAPLs) can contaminate soil and groundwater and may have the potential to pose explosive and other risks. In consideration of an acute LNAPL release scenario, we explore the value of a rapid remediation response, and the value of installing remediation infrastructure in close proximity to the spill location, in effecting greater recovery of LNAPL mass from the subsurface. For the first time, a verified three-dimensional multi-phase numerical framework and supercomputing resources was applied to explore the significance of in-time and in-place remediation actions. A sand aquifer, two release volumes and a low viscosity LNAPL were considered in key scenarios. The time of commencement of LNAPL remediation activities and the location of recovery wells were assessed requiring asymmetric computational considerations. The volume of LNAPL released considerably affected the depth of LNAPL penetration below the groundwater table, the radius of the plume over time and the recoverable LNAPL mass. The remediation efficiency was almost linearly correlated with the commencement time, but was a non-linear function of the distance of an extraction well from the spill release point. The ratio of the recovered LNAPL in a well located at the centre of the spill/release compared to a well located 5 m away was more than 3.5, for recovery starting only 7 days after the release. Early commencement of remediation with a recovery well located at the centre of the plume was estimated to recover 190 times more LNAPL mass than a one-month delayed commencement through a well 15 m away from the centre of the LNAPL plume. Optimally, nearly 40% of the initially released LNAPL could be recovered within two months of commencing LNAPL recovery actions.

Determination of specific LNAPL volumes in soils having a multimodal pore-size distribution.

In this paper we present modifications to previously published models for determining the specific volume of non-aqueous phase liquids (LNAPLs) in the subsurface at and near the groundwater table following a spill or leak from the soil surface. The modifications account for porous media having multimodal pore-size distributions as is often the case with tropical soils. Data from the literature are used to show that the use of multimodal pore-size distributions can lead to significantly different subsurface LNAPL specific volume predictions and possible LNAPL recovery rates, compared to when only unimodal pore-size distributions are considered. Differences of up to 200% are possible when the dual-porosity nature of the pore system is ignored, which can yield erroneous estimates of the time needed to remediate LNAPLs from contaminated areas when conventional systems are employed.

Sustainable risk-based analysis towards remediation of an aquifer impacted by crude oil spills.

Uncontrolled release of hydrocarbons from pipelines results in soil and groundwater contamination. However, due to the geo-environmental properties of the contaminated area, the remediation strategies might vary by light non-aqueous phase liquid (LNAPL) behaviors. In this study, a contaminated area with spilled oil from a pipeline was monitored. In the initial investigation in the 1980s, the contamination was reported in some citizen wells (CIZs), which resulted in drilling of 15 boreholes (BHs) across the Site from February 2001 to February 2007. Additionally, an area of around 0.24 km2 encompassing the LNAPL was inferred. The extension of plume in 2016-7 was monitored in this study, in which new farms were impacted by the contamination. Further, a conceptual model based on the previous information and current measured data was developed to better understand the behavior of the plume. The model showed that the Site is very complex, dipping towards the south, and the groundwater contains light hydrocarbons. Pumping tests, as a part of LNAPL remedial technology, were conducted by using three pumping wells (PWs), each accompanied by a monitoring well. Accordingly, a risk-based corrective action was implemented to eliminate and control unacceptable risks in a safe and timely manner. From the remediation approach, a monitoring plan in BHs and CIZs was suggested. In the case of receptors (humans and farms), clean-up of wells, tanks, and water channels as well as replacement of contaminated soils were highly regarded. Although the recent investigation and clean up monitoring wells showed that the LNAPL was very minimal, further steps in the receptor side should be taken prior to irrigation applications.

Towards characterizing LNAPL remediation endpoints.

Remediating sites contaminated with light non-aqueous phase liquids (LNAPLs) is a demanding and often prolonged task. It is vital to determine when it is appropriate to cease engineered remedial efforts based on the long-term effectiveness of remediation technology options. For the first time, the long term effectiveness of a range of LNAPL remediation approaches including skimming and vacuum-enhanced skimming each with and without water table drawdown was simulated through a multi-phase and multi-component approach. LNAPL components of gasoline were simulated to show how component changes affect the LNAPL's multi-phase behaviour and to inform the risk profile of the LNAPL. The four remediation approaches along with five types of soils, two states of the LNAPL specific mass and finite and infinite LNAPL plumes resulted in 80 simulation scenarios. Effective conservative mass removal endpoints for all the simulations were determined. As a key driver of risk, the persistence and mass removal of benzene was investigated across the scenarios. The time to effectively achieve a technology endpoint varied from 2 to 6 years. The recovered LNAPL in the liquid phase varied from 5% to 53% of the initial mass. The recovered LNAPL mass as extracted vapour was also quantified. Additional mass loss through induced biodegradation was not determined. Across numerous field conditions and release incidents, graphical outcomes provide conservative (i.e. more prolonged or greater mass recovery potential) LNAPL remediation endpoints for use in discussing the halting or continuance of engineered remedial efforts.

LNAPL transmissivity as a remediation metric in complex sites under water table fluctuations.

Water table fluctuations affect the recoverability of light non-aqueous phase liquid (LNAPL) petroleum hydrocarbons. LNAPL transmissivity (Tn) is being applied as an improved metric for LNAPL recoverability. In this paper, the applicability of Tn as a lagging and leading metric in unconsolidated aquifers under variable water table conditions was investigated. Tn values obtained through baildown testing and recovery data-based methods (skimming) were compared in three areas of a heterogeneous gasoline contaminated site in Western Australia. High-resolution characterisation methods were applied to account for differences in the stratigraphic profile and LNAPL distribution. The results showed a range of Tn from 0 m2/day to 2.13 m2/day, exhibiting a strong spatial and temporal variability. Additionally, observations indicated that Tn reductions may be more affected by the potentiometric surface elevation (Zaw) than by the application of mass recovery technologies. These observations reflected limitations of Tn as a lagging metric and a Remedial Endpoint. On the other hand, the consistency and accuracy of Tn as a leading metric was affected by the subsurface conditions. For instance, the area with a larger vertical LNAPL distribution and higher LNAPL saturations found Tn to be less sensitive to changes in Zaw than the other two areas during the skimming trials. Tn values from baildown and skimming tests were generally in a close agreement (less than a factor of 2 difference), although higher discrepancies (by a factor up to 7.3) were found, probably linked to a preferential migration pathway and Zaw. Under stable Zaw, Tn was found to be a relatively reliable metric. However, variable water table conditions affected Tn and caution should be exercised in such scenarios. Consequently, remediation practitioners, researchers and regulators should account for the nexus between Tn, LNAPL distribution, geological setting and temporal effects for a more efficient and sustainable management of complex contaminated sites.

Understanding complex LNAPL sites: Illustrated handbook of LNAPL transport and fate in the subsurface.

The goal of the paper is to highlight the management of the complexities and risks for light non-aqueous phase liquid (LNAPL) sites, and how the Illustrated Handbook of LNAPL Transport and Fate in the Subsurface (CL:AIRE, London. ISBN 978-1-905046-24-9. http://www.claire.co.uk/LNAPL; "LNAPL illustrated handbook") is useful guidance and a tool for professionals to understand these complexities and risks. The LNAPL illustrated handbook provides a clear and concise best-practice guidance document, which is a valuable decision support tool for use in discussions and negotiations regarding LNAPL impacted sites with respect to the risks of LNAPL. The LNAPL illustrated handbook is a user-friendly overview of the nature of LNAPL contamination in various geological settings including unconsolidated, consolidated, and fractured rock environments to best understand its fate and behavior leading to the appropriate management and/or remedial approach of the two major risks associated with a LNAPL source. As a source term, LNAPL has chemicals that form dissolved- and vapor-phase plumes, which are referred to as composition-based risks; and being a liquid there is the risk that the source may expand impacting a greater volume of the aquifer, which are referred to as saturation-based risks. There have been significant developments in recent years on the understanding of the complex behavior of LNAPL and associated groundwater and vapor plumes; however, the state of practice has often lagged these improvements in knowledge. The LNAPL illustrated handbook aids the site investigator, site owners, and regulators to understand these risks, and understand how these risks behave through better conceptual understanding of LNAPL transport and fate in the subsurface.

An assessment of subsurface contamination of an urban coastal aquifer due to oil spill.

Incidences of leakages of chemicals from underground oil storage tanks or oil-carrying pipelines have posed huge threat to the coastal aquifers around the world. One such leak was recently identified and notified by the people of Tondiarpet, Chennai, India. The assessment of the contamination level was done by obtaining electrical resistivity maps of the subsurface, drilling of 20 new borewells for soil and water analysis, and testing the water quality of 30 existing borewells. Samples were collected from the borewells, and observations were made that included parameters such as odor, moisture, contamination characteristics, lithology, groundwater level, thickness of the free product that are used to demarcate the extent of soil, and water contamination. Furthermore, a multigas detector was used to detect hydrocarbon presence as soil vapor. Moreover, to capture the transport of dissolved hydrocarbons, 10 samples were collected in the periphery of the study area and were analyzed for the presence of petroleum hydrocarbon and polyaromatic hydrocarbon. Analysis of the data indicated the presence of free-phase hydrocarbon in soil and groundwater close to the junction of Thiruvottiyur high (TH) road (TH) and Varadaja Perumal Koil (VPK) street. Although the contaminant plume is confined to a limited area, it has spread more to the southern and eastern side of the pipeline possibly due to continuous abstraction of groundwater by residential apartments. After cutting a trench along the VPK street and plotting of the plume delineation map, observations indicated that the source of the hydrocarbon leak is present in VPK street close to TH road. A multipronged strategy was suggested targeting the remediation of oil in various phases.

Comparison of bacterial and archaeal communities in depth-resolved zones in an LNAPL body.

Advances in our understanding of the microbial ecology at sites impacted by light non-aqueous phase liquids (LNAPLs) are needed to drive development of optimized bioremediation technologies, support longevity models, and develop culture-independent molecular tools. In this study, depth-resolved characterization of geochemical parameters and microbial communities was conducted for a shallow hydrocarbon-impacted aquifer. Four distinct zones were identified based on microbial community structure and geochemical data: (i) an aerobic, low-contaminant mass zone at the top of the vadose zone; (ii) a moderate to high-contaminant mass, low-oxygen to anaerobic transition zone in the middle of the vadose zone; (iii) an anaerobic, high-contaminant mass zone spanning the bottom of the vadose zone and saturated zone; and (iv) an anaerobic, low-contaminant mass zone below the LNAPL body. Evidence suggested that hydrocarbon degradation is mediated by syntrophic fermenters and methanogens in zone III. Upward flux of methane likely contributes to promoting anaerobic conditions in zone II by limiting downward flux of oxygen as methane and oxygen fronts converge at the top of this zone. Observed sulfate gradients and microbial communities suggested that sulfate reduction and methanogenesis both contribute to hydrocarbon degradation in zone IV. Pyrosequencing revealed that Syntrophus- and Methanosaeta-related species dominate bacterial and archaeal communities, respectively, in the LNAPL body below the water table. Observed phylotypes were linked with in situ anaerobic hydrocarbon degradation in LNAPL-impacted soils.

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.

An experimental multi-method approach to better characterize the LNAPL fate in soil under fluctuating groundwater levels.

Light-Non-Aqueous phase liquids (LNAPLs) are important soil contamination sources, and groundwater fluctuations may significantly affect their migration and release. However, the risk assessment remains complex due to the continuous three-phase fluid redistribution caused by water table level variations. Hence, monitoring methods must be improved to integrate better the LNAPL multi-compound and multi-phase aspects tied to the groundwater level dynamics. For this purpose, a lysimetric contaminated soil column (2 m3) combining in-situ monitoring (electrical permittivity, soil moisture, temperature, pH, Eh), direct water and gas sampling and analyses (GC/MS-TQD, µGC) in monitoring well, gas collection chambers, and suction probes) were developed. This experiment assesses in an integrated way how controlled rainfalls and water table fluctuation patterns may affect LNAPL vertical soil saturation distribution and release. Coupling these methods permitted the investigation of the effects of rainwater infiltration and water table level fluctuation on contaminated soil oxygen turnover, LNAPL contaminants' soil distribution and remobilization towards the dissolved and the gaseous phase, and the estimate of the LNAPL source attenuation rate. Hence, 7.5% of the contamination was remobilized towards the dissolved and gaseous phase after 120 days. During the experiment, groundwater level variations were responsible for the free LNAPL soil spreading and trapping, modifying dissolved LNAPL concentrations. Nevertheless, part of the dissolved contamination was rapidly biodegraded, leaving only the most bio-resistant components in water. This result highlights the importance of developing new experimental devices designed to assess the effect of climate-related parameters on LNAPL fate at contaminated sites.

Radon deficit technique applied to the study of the ageing of a spilled LNAPL in a shallow aquifer.

A recent diesel spill (dated January 2019 ± 1 month) in a refilling station is investigated by the Radon deficit technique. The primary focus was on quantifying the LNAPL pore saturation as a function of duration of ageing, and on proposing a predictive model for on-site natural attenuation. A biennial monitoring of the local fluctuating shallow aquifer has involved the saturated zone nine times, and the vadose zone only once. Rn background generally measured in external and upstream wells is elaborated further due to the site characteristics, using drilling logs and phreatic oscillations. Notably, this study marks the first application of the Rn deficit method to produce a detailed Rn background mapping throughout the soil depth. Simultaneously, tests are performed on LNAPL surnatant samples to study diesel ageing. In particular, they are focused on temporal variations of LNAPL viscosity (from an initial 3.90 cP to 8.99 cP, measured at 25 °C, after 34 months), and Rn partition coefficient between the pollutant and water (from 47.7 to 80.2, measured at 25 °C, after 14 months). Rn diffusion is also measured in different fluids (0.092 cm2 s-1, 1.14 × 10-5 cm2 s-1, and 2.53 × 10-6 cm2 s-1 at 25 °C for air, water and LNAPL, respectively) directly. All parameters and equations utilized during this study are introduced, discussing their influence on Radon deficit technique from a theoretical point of view. Experimental findings are used to mitigate the effect of LNAPL ageing and of phreatic oscillations on determination of LNAPL saturation index (S.I.LNAPL). Finally, S.I.LNAPL dataset is discussed and elaborated to show the pollutant attenuation across subsurface over time, induced by natural processes primarily. The proposed predictive model for on-site natural attenuation suggests a half-removal time of one year and six months. The significance of such models lies in their capability to assess site-specific reactions to pollutants, thereby enhancing the effectiveness of remediation efforts over time. These experimental findings may offer a novel approach to application of Rn deficit technique and to environmental remediation of persistent organic compounds.

An integrated evaluation of bioenhanced in situ LNAPL dissolution.

Performance evaluation of in situ bioremediation processes in the field is difficult due to uncertainty created by matrix and contaminant heterogeneity, inaccessibility to direct observation, expense of sampling, and limitations of some measurements. The goal of this research was to develop a strategy for evaluating in situ bioremediation of light nonaqueous-phase liquid (LNAPL) contamination and demonstrating the occurrence of bioenhanced LNAPL dissolution by: (1) integrating a suite of analyses into a rational evaluation strategy; and (2) demonstrating the strategy's application in intermediate-scale flow-cell (ISFC) experiments simulating an aquifer contaminated with a pool of LNAPL (naphthalene dissolved in dodecane). Two ISFCs were operated to evaluate how the monitored parameters changed between a "no bioremediation" scenario and an "intrinsic in situ bioremediation" scenario. Key was incorporating different measures of microbial activity and contaminant degradation relevant to bioremediation: contaminant loss; consumption of electron acceptors; and changes in total alkalinity, pH, dissolved total inorganic carbon, carbon-stable isotopes, microorganisms, and intermediate metabolites. These measurements were integrated via mass-flux modeling and mass-balance analyses to document that in situ biodegradation of naphthalene was strongly accelerated in the "intrinsic in situ bioremediation" scenario versus "no bioremediation." Furthermore, the integrated strategy provided consistent evidence of bioenhancement of LNAPL dissolution through intrinsic bioremediation by a factor of approximately 2 due to the biodegradation of the naphthalene near the pool/water interface.

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.

Quantitative expression of LNAPL pollutant concentrations in capillary zone by coupling multiple environmental factors based on random forest algorithm.

The capillary zone plays a crucial role in migration and transformation of pollutants. Light nonaqueous liquids (LNAPLs) have become the main organic pollutant in soil and groundwater environments. However, few studies have focused on the concentration distribution characteristics and quantitative expression of LNAPL pollutants within capillary zone. In this study, we conducted a sandbox-migration experiment using diesel oil as a typical LNAPL pollutant, with the capillary zone of silty sand as the research object. The variation characteristics of LNAPL pollutants (total petroleum hydrocarbon) concentration and environmental factors (moisture content, electrical conductivity, pH, and oxidationreduction potential) were essentially consistent at different locations with the same height. These characteristics differed within range of 10.0-50.0 cm and above 60.0 cm from groundwater. A model for quantitative expression of concentrations was constructed by coupling multiple environmental factors of 968 sets-7744 data via random forest algorithm. The goodness of fit (R2) for both training and test sets was greater than 0.90, and the mean absolute percentage error (MAPE) was less than 16.00 %. The absolute values of relative errors in predicting concentrations at characteristic points were less than 15.00 %. The constructed model can accurately and quantitatively express and predict concentrations in capillary zone.

Assessing the Natural Source Zone Depletion of a Petroleum-Contaminated Clayey Soil Site in Southern China Combining Concentration Gradient Method and Metagenomics.

Natural source zone depletion (NSZD) is the main process of LNAPL (Light Non-Aqueous Phase Liquid) removal under natural conditions. The NSZD rates assessed ranged from 0.55 to 11.55 kg·m-2·a-1 (kilograms per square meter per year) in previous studies. However, most of these data were obtained from sandy sites, with few clayey sites. To gain knowledge of NSZD in clayey soil sites, the study assessed the NSZD of a petroleum hydrocarbon-contaminated clayey soil site in China, combining the concentration gradient method with metagenomic sequencing technology. The results show that the abundance of methane-producing key enzyme mcrA gene in the source zone was more abundant than in background areas, which suggests that there was methanogenesis, the key process of NSZD. The concentration gradients of oxygen and carbon dioxide existed only in shallow soil (<0.7 m), which suggests that there was a thin methane oxidation zone in the shallow zone. The calculated NSZD rates range from 0.23 to 1.15 kg·m-2·a-1, which fall within the moderate range compared to previous NSZD sites. This study expands the knowledge of NSZD in clayey soil and enriches the attenuation rate data for contaminated sites, which is of significant importance in managing petroleum contaminants.

Groundwater and soil contamination by LNAPL: State of the art and future challenges.

Contamination by Light Non-Aqueous Phase Liquids (LNAPL) represents a challenge due to the difficulties encountered in its underground assessment and recovery. The major risks arising from subsoil LNAPL accumulation face human health and environment, gaining a social relevance also in the frame of a continuously changing climate. This paper reports on a literature review about the underground contamination by LNAPL, with the aims of providing a categorization of the aspects involved in this topic, analyzing the current state of the art, underlying potential lacks and future perspectives. The review was focused on papers published in the 2012-2022 time-interval, in journals indexed in Scopus and WoS databases, by querying "LNAPL" within article title, abstract and/or key words. 245 papers were collected and classified according to three "key approaches" -namely laboratory activity, field based-data studies and mathematical simulations- and subordinate "key themes", so to allow summarizing and commenting the main aspects based on the application setting, content and scope. Results show that there is a wide experience on plume dynamics and evolution, detection and monitoring through direct and indirect surveys, oil recovery and natural attenuation processes. Few cues of innovations were found regarding both the use of new materials and/or specific field configuration for remediation, and the application of new techniques for plume detection. Some limitations were found in the common oversimplification of the polluted media in laboratory or mathematical models, where the contamination is set within homogeneous porous environments, and in the low number of studies focused on rock masses, where the discontinuous hydraulic behavior complicates the address and modeling of the issue. This paper represents a reference for a quick update on the addressed topic, along with a starting point to develop new ideas and cues for the advance in one of the greatest environmental banes of the current century.