Elevated Radium Activity in a Hydrocarbon-Contaminated Aquifer.

Hydrocarbon spills that reach the subsurface can modify aquifer geochemical conditions. Biogeochemical zones typically form proximal to the source zone that include iron (Fe(III)) and manganese (Mn(III/IV)) (hydr)oxide reduction, with potential to release associated geogenic contaminants to groundwater. Here, multi-level monitoring systems are used to investigate radium (226Ra, 228Ra) activities in an aquifer contaminated with a mixture of chlorinated solvents, ketones, and aromatics occurring as a dense non-aqueous phase liquid in the source zone. 226Ra activities are up to 10 times higher than background 60 m downgradient from the source zone, where pH is lower, total dissolved solid concentrations are higher, and conditions are methanogenic. Correlations indicate that Fe and Mn (hydr)oxide reduction and sorption site competition are likely responsible for elevated Ra activities within the dissolved phase plume. 226Ra activities return to background within the Fe(III)/SO42--reducing zone 600 m downgradient from the source, near the middle of the dissolved phase plume. Geochemical models indicate that sorption to secondary phases (e.g., clays) is important in sequestering Ra within the plume. Although maximum Ra activities within the plume are well below the U.S. drinking water standard, elevated activities compared to background emphasize the importance of investigating Ra and other trace elements at hydrocarbon-impacted sites.

A review of the occurrence, distribution, and impact of bitumen seeps on soil and groundwater in parts of southwestern Nigeria.

The impact of bitumen components on soil and groundwater resources is of environmental importance. Contaminants' influx into the environment from bitumen components through anthropogenic activities such as exploration, mining, transportation, and usage of bitumen in all its forms have been reported globally. However, gaps exist in the geogenic occurrence of bitumen in the shallow subsurface such as in southwest Nigeria, contaminating the soil and groundwater resources. This review presents in situ bitumen seeps as a source of geogenic soil and groundwater contaminants in southwestern Nigeria. We conducted a systematic review of literatures based on defined selection criteria. We derived information on the state of knowledge about bitumen seep occurrences and distribution in southwestern Nigeria. Also, the processes that exacerbate bitumen contaminants' influx into soil and groundwater were enunciated. At the same time, case examples highlighted areas for possible in situ bitumen contamination studies in Nigeria. The results of this review showed that a multidisciplinary approach has been employed to assess and monitor the contaminants resulting from the various activities involving the exploitation and application of bitumen in Nigeria. These studies emphasize bitumen contaminants as emanating from anthropogenic sources. The results also suggested that bitumen studies have been mainly exploratory to improve the understanding of the economic potential of the hydrocarbon reserve. Also, recent advances in bitumen contaminants studies accounted for the heterogeneous nature of the bitumen. This allows for the optimized categorization of the mechanism and processes undergone by the different bitumen components when released as environmental contaminants. However, a knowledge gap exists in characterizing and understanding the effects of in situ bitumen seeps as a geogenic source of soil and groundwater contamination. This review identifies the possibility of geogenic soil and groundwater contamination by in situ bitumen seeps in the coastal plain sand of the Dahomey basin in southwestern Nigeria. The impact of the bitumen contaminants on the environment was discussed, while methods for accessing the occurrence and distribution of the bitumen contaminants were highlighted.

Study of creosote transport properties in sandy and clay soils.

Creosote is an organic pollutant formed by a complex mixture of highly toxic and carcinogenic compounds and classified as a dense non-aqueous phase liquid (DNAPL). Its migration depends on media and fluid properties that control the multiphase flow in the subsurface. Residual saturation and hydraulic conductivity are essential parameters to accurately simulate fluid displacement in porous media. This work shows the behavior of creosote in porous medium for sandy and clay soils, collected in a contaminated area in the state of São Paulo, Brazil. Creosote retention was evaluated and compared to water. The retention curve parameters were obtained based on van Genuchten and Brooks and Corey models. The hydraulic conductivities of creosote and water are presented for both soils. The results show that, in the clay soil, water was more retained than creosote, while in the sandy soil, creosote retention was higher. The hydraulic conductivity values obtained in the clay soil show a difference of two orders of magnitude between creosote and water. Although creosote is a viscous fluid, it presents considerable mobility in the clay soil, which is relevant in remediation processes. This study advances our knowledge about DNAPL behavior in clay and sand, and no other study of creosote parameters in these porous media was found. A more accurate estimate of the time required for a liquid spill to reach groundwater can then be predicted, so that appropriate actions can be taken and risk management can be carried out.

Abatement of chlorobenzenes in aqueous phase by persulfate activated by alkali enhanced by surfactant addition.

Sites polluted by dense non-aqueous phases (DNAPLs) constitute an environmental concern. In situ chemical oxidation (ISCO) application is limited since oxidation often occurs in the aqueous phase and contaminants are usually hydrophobic. In this work, ISCO enhanced by the surfactant addition (S-ISCO) was studied for a complex liquid mixture of chlorinated organic compounds (COCs) using persulfate (PS) activated by alkali (PSA) as oxidant and Emulse-3® as a commercial non-ionic surfactant. The reaction between E3 and PSA was investigated in the absence and presence of solubilized COCs in the following concentration ranges: COCs 1.2-50 mM, PS 84-336 mM, NaOH:PS molar ratio of 2, and surfactant concentration 1-10 g·L-1. In the experiments carried out in the absence of COCs, the unproductive consumption of PS was studied. The higher the surfactant concentration, the lower the ratio PS consumed to the initial surfactant concentration due to more complex micelle structures hindering the oxidation of surfactant molecules. This hindering effect was also noticed in the oxidation of solubilized COCs. The reduction of chlorobenzenes by PSA was negligible at surfactant concentrations above 2.5 g·L-1, independently of the COCs concentration solubilized. Instead, a surfactant concentration of about 1 and PS concentration of 168 mM yielded a significant decrease in the time required to abate a mass of DNAPL, compared with an ISCO process, with a bearable increase in the unproductive consumption of PS.

Acute Toxicity Evaluation of Lindane-Waste Contaminated Soils Treated by Surfactant-Enhanced ISCO.

The discharge of lindane wastes in unlined landfills causes groundwater and soil pollution worldwide. The liquid waste generated (a mixture of 28 chlorinated organic compounds, COCs) constitutes a dense non-aqueous phase liquid (DNAPL) that is highly persistent. Although in situ chemical oxidation (ISCO) is effective for degrading organic pollutants, the low COCs solubility requires high reaction times. Simultaneous injection of surfactants and oxidants (S-ISCO) is a promising technology to solve the limitation of ISCO treatment. The current work studies the remediation of highly polluted soil (COCs = 3682 mg/kg) obtained at the Sardas landfill (Sabiñáñigo, Spain) by ISCO and S-ISCO treatments. Special attention is paid to acute soil toxicity before and after the soil treatment. Microtox®, modified Basic Solid-Phase Test (mBSPT) and adapted Organic Solvent Sample Solubilization Test (aOSSST) were used for this scope. Persulfate (PS, 210 mM) activated by alkali (NaOH, 210 mM) was used in both ISCO and S-ISCO runs. A non-ionic and biodegradable surfactant selected in previous work, Emulse®3 (E3, 5, and 10 g/L), was applied in S-ISCO experiments. Runs were performed in soil columns filled with 50 g of polluted soil, with eight pore volumes (Pvs) of the reagents injected and 96 h between successive Pv injections. The total treatment time was 32 days. The results were compared with those corresponding without surfactant (ISCO). After remediation treatments, soils were water-washed, simulating the conditions of groundwater flux in the subsoil. The treatments applied highly reduced soil toxicity (final soil toxicity equivalent to that obtained for non-contaminated soil, mBSPT) and organic extract toxicity (reduction > 95%, aOSSST). Surfactant application did not cause an increase in the toxicity of the treated soil, highlighting its suitability for full-scale applications.

Enhanced reductive dechlorination of trichloroethene in an acidic DNAPL impacted aquifer.

A field pilot test was conducted using an emulsified vegetable oil (EVO) and colloidal magnesium hydroxide [Mg(OH)2] formulation to enhance reductive dechlorination of dense non-aqueous phase liquid (DNAPL) trichloroethene (TCE) in an acidic (pH < 4), heterogeneous aquifer. The field test consisted of i) a single well injection test to evaluate Mg(OH)2 distribution and ii) installation of two EVO-Mg(OH)2 permeable reactive barriers (PRBs; PRB-1 & PRB-2) at varying distances downgradient of the DNAPL source area. Distribution of Mg(OH)2 was observed up to 2.3 m away from the injection point within a permeable coarse sand layer; however, Mg(OH)2 transport in the overlying clayey-silty sand was minimal. Downgradient of the PRBs, colloidal Mg(OH)2 increased the pH of the coarse sand to levels appropriate for biological reductive dechlorination (pH >∼5); however, some settling of Mg(OH)2 in the injection wells generated persistent high pH (∼9-10) within the PRBs. A redesigned suspension of colloidal Mg(OH)2 was tested and proved to be more effective at raising aquifer pH without an excessive rise in pH within the PRBs. At PRB-1 (located closest to the DNAPL source area), limited TCE biodegradation was observed due to the influx of high TCE concentrations (up to 400 mg/L) and inhibition of dechlorinating bacteria. At PRB-2 (located 25 m downgradient of the DNAPL source area), TCE concentrations were much lower (13-26 mg/L) and production of cis-1,2-dichloroethene (cDCE) and some vinyl chloride (VC) was observed. Subsequent bioaugmentation with a commercial dechlorinating culture at PRB-2 improved conversion of cDCE to VC and ethene at downgradient monitoring wells over the duration of the study. These results emphasize the importance of PRB location (relative to the DNAPL source), base selection for pH adjustment, source strength, and local heterogeneities for the design and long-term performance of ERD in acidic DNAPL-impacted aquifers.

Persistence of a Groundwater Contaminant Plume after Hydraulic Source Containment at a Chlorinated-Solvent Contaminated Site.

The objective of this study was to characterize the behavior of a groundwater contaminant (trichloroethene) plume after implementation of a source-containment operation at a site in Arizona. The plume resides in a quasi three-layer system comprising a sand/gravel unit bounded on the top and bottom by relatively thick silty clayey layers. The system was monitored for 60 months beginning at start-up in 2007 to measure the change in contaminant concentrations within the plume, the change in plume area, the mass of contaminant removed, and the integrated contaminant mass discharge. Concentrations of trichloroethene in groundwater pumped from the plume extraction wells have declined significantly over the course of operation, as have concentrations for groundwater sampled from 40 monitoring wells located within the plume. The total contaminant mass discharge associated with operation of the plume extraction wells peaked at 0.23 kg/d, decreased significantly within one year, and thereafter began an asymptotic decline to a current value of approximately 0.03 kg/d. Despite an 87% reduction in contaminant mass and a comparable 87% reduction in contaminant mass discharge for the plume, the spatial area encompassed by the plume has decreased by only approximately 50%. This is much less than would be anticipated based on ideal flushing and mass-removal behavior. Simulations produced with a simplified 3-D numerical model matched reasonably well to the measured data. The results of the study suggest that permeability heterogeneity, back diffusion, hydraulic factors associated with the specific well field system, and residual discharge from the source zone are all contributing to the observed persistence of the plume, as well as the asymptotic behavior currently observed for mass removal and for the reduction in contaminant mass discharge.

Enhancing remediation of residual DNAPL in multilayer aquifers: Post-injection of alcohol-surfactant-polymer mixtures.

Although polymer-surfactant injection is an effective remediation technology for multilayer aquifers contaminated by Dense Non-Aqueous Phase Liquids (DNAPL), the existence of residual DNAPL after treatment is inevitable. This study evaluates the efficiency of the post-injection of alcohol-surfactant-polymer (ASP) mixtures containing 1-propanol/1-hexanol, sodium dodecylbenzenesulfonate (SDBS), and xanthan in enhancing remediation of residual DNAPL in layered systems. A range of experimental devices, including batch, rheological measurements, centimetric 1D column, and decametric 2D tank experiments, were employed. Batch experiments revealed that the inclusion of 1-hexanol swelled the DNAPL volume due to alcohol partitioning. Conversely, with only 1-propanol present in the alcohol-surfactant (AS) mixture, DNAPL dissolved in the aqueous phase. The co-presence of 1-hexanol along with 1-propanol in AS mixture favored 1-propanol's partitioning into the DNAPL phase. Column experiments, following primary xanthan-SDBS (XS) injections, demonstrated that ASP mixtures with 1-hexanol (regardless of presence of 1-propanol) underwent a mobilization mechanism. DNAPL appeared in the effluent as an organic phase after the post-injection of 0.3 pore-volumes (PV), by a reduction trend in its density. In contrast, mixtures with solely 1-propanol exhibited a solubilization mechanism, with DNAPL dissolving in the aqueous phase and emerging in the effluent after approximately 1 PV. 2D tank experiments visualized mobilization and solubilization mechanisms in multilayered systems. Post-injection of the ASP mixture with solely 1-propanol led to DNAPL solubilization, demonstrated by a dark zone of varied DNAPL concentrations, followed by a clearer white zone indicating significant DNAPL dissolution. Injecting ASP mixture containing both 1-propanol and 1-hexanol mobilized swollen DNAPL ganglia throughout layers, with these droplets coalescing and migrating to the recovery point. The darkness of mobilized droplets was faded as more DNAPL was recovered. The solubilization ASP mixture enhanced the recovery factor by 0.02 while the mobilization ASP mixture led to a 0.08 increase in the recovery factor.

Sustainable lindane waste remediation: Surfactant-driven residual DNAPL extraction and oxidation in a real landfill (LIFE SURFING).

The LIFE SURFING Project was carried out at the Bailin Landfill in Sabiñánigo, Spain (2020-2022), applying Surfactant Enhanced Aquifer Remediation (SEAR) and In Situ Chemical Oxidation (S-ISCO) in a 60-meter test cell beneath the old landfill, to remediate a contaminated aquifer with dense non-aqueous phase liquid (DNAPL) from nearby lindane production. The project overcame traditional extraction limitations, successfully preventing groundwater pollution from reaching the river. In spring 2022, two SEAR interventions involved the injection of 9.3 m3 (SEAR-1) and 6 m3 (SEAR-2) of aqueous solutions containing 20 g/L of the non-ionic surfactant E-Mulse 3®, with bromide (around 150 mg/L) serving as a conservative tracer. 7.1 and 6.0 m3 were extracted in SEAR-1 and SEAR-2, respectively, recovered 60-70 % of the injected bromide and 30-40 % of the surfactant, confirming surfactant adsorption by the soil. Approximately 130 kg of DNAPL were removed, with over 90 % mobilized and 10 % solubilized. A surfactant-to-DNAPL recovery mass ratio of 2.6 was obtained, a successful value for a fractured aquifer. In September 2022, the S-ISCO phase entailed injecting 22 m3 of a solution containing persulfate (40 g/L), E-Mulse 3® (4 g/L), and NaOH (8.75 g/L) in pulses over 48 h, oxidizing around 20 kg of DNAPL and ensuring low toxicity levels after that. Preceding the SEAR and S-ISCO trials, 2020 and 2021 were dedicated to detailed groundwater flow characterizations, including hydrological and tracer studies. These preliminary investigations allowed the design of a barrier zone between 317 and 557 m from the test cell and the river, situated 900 m away. This zone, integrating alkali dosing, aeration, vapor extraction, and oxidant injection, effectively prevented the escape of fluids to the river. Neither surfactants nor contaminants were detected in river waters post-treatment. The absence of residual phase in test cell wells and reduction of chlorinated compound levels in groundwater were noticed till one year after S-ISCO.

2D model of groundwater flow and total dissolved HCH transport through the Gállego alluvial aquifer downstream the Sardas landfill (Huesca, Spain).

The organic pollutants disposed at the Sardas landfill in Sabiñánigo (Huesca, northeastern Spain) by the INQUINOSA lindane factory have reached the Gállego alluvial aquifer and could affect the Sabiñánigo reservoir. The daily oscillations of the reservoir water level produce a tidal effect on the piezometric heads of the aquifer. These oscillations are transmitted in a damped way with a time lag, thus attesting that the silting sediments of the reservoir and the natural silts of the Gállego alluvial are interposed between the reservoir water and the layer of sands and gravels. A 2D finite element groundwater flow and total dissolved hexachlorocyclohexane (HCH) transport model through the Gállego alluvial aquifer is presented here. The flow model was constructed to: (1) Quantify the tidal effect, produced by the daily fluctuations of the reservoir water level on the aquifer; (2) Estimate the hydrodynamic parameters of the layer of sands and gravels; and 3) Estimate the vertical hydraulic conductivity of the silting sediments and silts; and (4) Quantify aquifer/reservoir interactions. The flow model reproduces the dynamics of the tidal effect and attests that groundwater velocity and flow direction changes daily in response to the oscillations of the reservoir level. Model results reproduce the measured well hydrographs and the Darcy velocity derived from tracer tests and confirm the validity of the conceptual model. The transport model of total dissolved HCH simulates the time evolution of the contaminant plume. The computed concentrations of total dissolved HCH and the contaminant mass outflux are very sensitive to changes in the source terms and the distribution coefficient, Kd of HCH. The best fit to the measured HCH plumes in September 2010 and December 2020 is obtained with a Kd ranging from 1 to 3 L/kg. The computed flux of dissolved HCH leaving the Sardas site in 2020 towards the Sabiñánigo reservoir ranges from 0.6 kg/year for Kd = 3 L/kg to 3.1 kg/year for Kd = 1 L/kg. The findings of this study will be most useful for planning and designing remedial and containment actions at the Sardas site and other similar lindane-affected sites.

Remediation of groundwater polluted with lindane production wastes by conductive-diamond electrochemical oxidation.

This work studies the remediation of groundwater saturated with dense non-aqueous phase liquid (DNAPL) from lindane production wastes by electrochemical oxidation. DNAPL-saturated groundwater contains up to 26 chlorinated organic compounds (COCs), including different isomers of hexachlorocyclohexane (HCH). To do this, polluted groundwater was electrolysed using boron-doped diamond (BDD) and stainless steel (SS) as anode and cathode, respectively, and the influence of the current density on COCs removal was evaluated in the range from 5 to 50 mA cm-2. Results show that current densities higher than 25 mA cm-2 lead to the complete removal and mineralisation of all COCs identified in groundwater. The higher the current density, the higher the COCs removal rate. At lower current densities (5 mA cm-2), chlorobenzenes were completely removed, and degradations above 90 % were reached for COCs with more than five chlorine atoms in their molecules. The use of BDD anodes promotes the electrochemical generation of powerful reactive species, such as persulfate, hypochlorite or hydroxyl radicals, that contribute to the degradation and mineralisation of COCs. The applied current density also influences the generation of these species. Finally, no acute toxicity towards Vibrio fischeri was observed for the treated groundwater after the electrochemical oxidation performed at 5 and 10 mA cm-2. These findings demonstrate that electrochemical oxidation with BDD anodes at moderate current densities is a promising alternative for the remediation of actual groundwater contaminated with DNAPLs.

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.

Time-lapse dielectric properties monitoring of the flow cell during DNAPL contamination and remediation processes by full-waveform inversion of GPR data using particle swarm optimization: A laboratory study.

This study presents the monitoring of the contamination and remediation processes of an aquifer system using the ground-penetrating radar (GPR) method. To achieve this, periodic GPR measurements were performed on a flow cell, which was established to simulate aquifer contamination and remediation scenarios. The exterior of the flow cell was made of plexiglas, and a small hole was created at the top center to inject Dense Non-aqueous Phase Liquid (DNAPL) contamination. To study contaminant distribution and remediation processes, DNAPL Trichloroethylene (TCE) was used as the groundwater contaminant. Methyl-beta-cyclodextrin (MCD) was used as remediation agent. The interior of the flow cell was packed with two different sand grain size distributions: low permeability sand along the bottom and a higher permeability sand along the top. Common offset GPR measurements were performed along the top plane of the flow cell. The GPR measurements were conducted periodically over a total duration of 66 days, encompassing the phases prior to injecting DNAPL TCE, after injection of DNAPL TCE, and during the remediation process using MCD. Time-lapse GPR data were analyzed using 1D and 2D plots. In addition, to evaluate and monitor the contamination and remediation processes within the flow cell, central traces of the time-lapse GPR dataset were inverted by full-waveform inversion to estimate the dielectric properties of the layers and the depth by Particle Swarm Optimization (PSO). To utilize PSO, a forward model calculation using 1D finite difference in time domain adapted to PSO algorithm to generate theoretical GPR traces to compare the theoretical model GPR traces to the measured GPR traces as a "goodness of fit" metric. The electrical conductivity, relative dielectric permittivity, relative magnetic permeability, and depth of the layer were estimated by PSO of the GPR data. The results of the inversion process indicated a significant change in the estimated electrical conductivity values for the post TCE DNAPL contamination stage and the remediation stage. In addition, to support the inversion results, contaminant mass removal was quantified using moment analysis from dissolved-phase contaminant concentrations collected from the flow cell over time. According to the mass recovery calculation by moment analysis, which was collected via an outlet from the flow cell, approximately 38 % of the injected DNAPL TCE mass was removed by enhanced dissolution from the representative aquifer domain of the flow cell during the remediation stage of the experiment.

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.

Optimized survey design for the joint use of direct current resistivity and induced polarization: Monitoring of DNAPL source zone evolution at a virtual field site.

The combined application of direct current (DC) resistivity and induced polarization (IP) methods, referred to as combined DCIP method, has gained popularity for characterizing the critical zone dynamic processes such as dense non-aqueous phase liquids (DNAPLs) spreading at contaminated sites. Large-scale DCIP surveys typically require considerable durations, necessitating optimized survey designs to enhance survey resolution while controlling time and labor costs. However, to date, approaches to optimize geoelectrical survey design have focused solely on DC applications, and the efficiency of optimized survey designs for combined DCIP is yet to be investigated. Moreover, as subsurface heterogeneity would impact the geophysical observations, most field-scale numerical DCIP studies have still been conducted at artificial sites that lacked realistic aquifer heterogeneity, which could affect the validity of the DCIP survey evaluations. In this work, a virtual geoenvironmental field site based on high-resolution real aquifer analog was created to simulate a DNAPL evolution scenario with simultaneous monitoring by DCIP survey, employing both the optimized survey design and popular non-optimized survey designs (Wenner, Wenner-Schlumberger, Dipole-Dipole arrays). Results show that the optimized survey with prior information improves the monitoring accuracy of DNAPL source zone (SZ) by 8 to 19 % with respect to different DCIP characteristics (conductivity, chargeability, normalized chargeability, and relaxation time). Another ideal numerical test indicates that the optimized survey shows up to an 83 % reduction in measurement time compared to the conventional survey, while maintaining the same subsurface image resolution. Additionally, the optimized surveys designed without or with limited prior information were also shown to be more efficient than conventional survey for imaging the entire subsurface space. The findings in this study highlight the immense potential of optimized survey design methods for enhancing the efficiency of DCIP surveys on subsurface contaminants and hydrological processes.

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.

A comparative study of DNAPL migration and transformation in confined and unconfined groundwater systems.

To explore the migration and transformation process of dense non-aqueous liquid (DNAPL) pollutants' multiphase flow, specifically nitrobenzene (NB), in confined groundwater (CG) versus unconfined groundwater (UG), a two-dimensional sandbox experimental device was designed and constructed. This involved constructing a vadose zone-UG- aquitard-CG structure, which was then subjected to different scenarios. Real-time analysis and numerical simulation methods were established and employed, with a particular focus on the detailed investigation results of actual contaminated site. The study found that when the same amount of NB was injected, the special structure of the CG layer resulted in a more pronounced reverse diffusion of NB in both the dissolved and NAPL phases. This was especially true for the dissolved phase, which was more likely to diffuse reversely. Meanwhile, CG did not directly interact with the vadose zone, and there was no loss of gas phase NB after the leakage in CG. As a result, higher concentrations of dissolved phase NB were generated, leading to the emergence of a larger area of NB contaminant plumes with CG flow. Importantly, the simulation study of the actual site and the laboratory experimental results were found to be validated, further validating the conclusion that direct leakage of NB into CG results in a higher concentration and larger area of dissolved phase contaminant plume, causing more serious pollution to the groundwater environment.

Comprehensive study of acute toxicity using Microtox® bioassay in soils contaminated by lindane wastes.

This research studies the acute toxicity of real contaminated soils (topsoil and subsoil) with hazardous chlorinated organic compounds (COCs) from lindane manufacturing wastes. The Microtox® bioassay was used to determine the toxicity of soils (modified Basic Solid Phase Test), soil elutriates (Basic Test), and organic extracts (adapted Organic Solvent Sample Solubilization Test), in which hydrophobic organic compounds are soluble. The acute toxicity of these persistent contaminants (hexachlorocyclohexanes, HCH isomers, as particulate matter in topsoil, and COCs, from dense non-aqueous phase liquid, DNAPL, in subsoil) and the commercial compounds were also measured. Soils tested showed different contaminant levels (topsoil: 0.9-1149 mg/kg and subsoil: 20-9528 mg/kg). Soil contaminants distribution, concentration and acute toxicity were highly related to the contamination source (HCHs or DNAPL). Soils, organic extracts, and subsoil elutriates presented high toxicity, highlighting the need for remediation of these sites. EC50 was calculated in the three-test applied for the soils tested. EC50 vs. COCs concentration in soils and soil elutriates showed an asymptotic trend, explained by the low pollutants solubility in the aqueous phase. Contrarily, EC50 vs. soil COCs concentration was more linear in the case of the organic extracts. This test was the most reliable from statistical analysis. The three methods reveal interesting and complementary information and are necessary for a complete overview of the acute toxicity of contaminated soils.

Characterization of DNAPL source zones in clay-sand media via joint inversion of DC resistivity, induced polarization and borehole data.

Toxic organic contaminants in groundwater are pervasive at many industrial sites worldwide. These contaminants, such as chlorinated solvents, often appear as dense non-aqueous phase liquids (DNAPLs). To design efficient remediation strategies, detailed characterization of DNAPL Source Zone Architecture (SZA) is required. Since invasive borehole-based investigations suffer from limited spatial coverage, a non-intrusive geophysical method, direct current (DC) resistivity, has been applied to image the DNAPL distribution; however, in clay-sand environments, the ability of DC resistivity for DNAPLs imaging is limited since it cannot separate between DNAPLs and surrounding clay-sand soils. Moreover, the simplified parameterization of conventional inversion approaches cannot preserve physically realistic patterns of SZAs, and tends to smooth out any sharp spatial variations. In this paper, the induced polarization (IP) technique is combined with DC resistivity (DCIP) to provide plausible DNAPL characterization in clay-sand environments. Using petrophysical models, the DCIP data is utilized to provide tomograms of the DNAPL saturation (SN) and hydraulic conductivity (K). The DCIP-estimated K/SN tomograms are then integrated with borehole measurements in a deep learning-based joint inversion framework to accurately parameterize the highly irregular SZA and provide a refined DNAPL image. To evaluate the performance of the proposed approach, we conducted numerical experiments in a heterogeneous clay-sand aquifer with a complex SZA. Results demonstrate the standalone DC resistivity method fails to infer the DNAPL in complex clay-sand environments. In contrast, the combined DCIP technique provides the necessary information to reconstruct the large-scale features of K/SN fields, while integrating DCIP data with sparse but accurate borehole data results in a high resolution characterization of the SZA.

Break-up and mobilization of DNAPL by acoustic excitation: Experimental evidence and pore network modeling.

Dense non-aqueous phase liquids (DNAPLs) are long-term groundwater contaminants due to their high toxicity and slight solubility in water. The use of acoustic waves to remobilize trapped ganglia in subsurface porous systems have some advantages over pre-existing solutions including eliminating the bypassing effect and new environmental hazards. Designing an effective acoustically assisted remediation method for such purposes relies on understanding the underlying mechanisms and developing validated models. In this work, pore-scale microfluidic experiments were run to investigate the interplay between break-up and remobilization under sonication at different levels of flow rate and wettability conditions. Based on the experimental observation and pore-scale physical characteristics, a pore network model was developed and verified against the experimental results. Such a model was developed based on a two-dimensional network and scaled up to three-dimensional networks. In the experiments, processing of two-dimensional images showed that acoustic waves can remobilize trapped ganglia. The other observed effect of vibration is to break up blobs and reduce the mean ganglia size. Recovery enhancements were greater in hydrophilic micromodels as compared to hydrophobic system. A strong correlation was found between the remobilization and breakup indicating that the trapped ganglia are breaking up due to acoustic stimulation firstly and then a background viscous force may get them flowing under the new generated fluid distribution. In modeling, the simulation results of residual saturation reasonably matched with experimental observations. The differences between the prediction by the model and the experimental data at verification points is less than 2% for data before and after the acoustic excitation. The transitions from three-dimensional simulations were used to propose a modified capillary number. This study gives a better understanding of the mechanisms behind the effect of acoustic waves in porous media and provides a predictive tool for evaluating enhancement in fluid displacement.