Nonaqueous Phase Research Articles

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.

Solubility and interfacial tension models for CO2–brine systems under CO2 geological storage conditions

Thermodynamic properties of the CO2–brine pseudo-binary system are essential for the design of geological carbon storage (GCS) projects, especially those utilizing saline aquifers. The gas–liquid–solid interactions manifest in the interfacial tensions (IFTs) and contact angle determine the injectability, sealing capacity, and storage security of the GCS process. Dissolution of CO2 in the reservoir brine occurs throughout the entire GCS process, leading to enhanced storage capacity but also to acidification of the brine, possibly leading to reservoir or seal damage. Two of the most important thermodynamic properties of the fluids are the mutual solubility and the IFT of the CO2–brine pseudo-binary system. In this work, we report a new correlative model for the IFT between CO2- and water-rich phases over wide ranges of temperature (273 to 473 K) and pressure (up to 100 MPa). The model is parameterized for brines comprising any combinations of sodium, potassium, calcium and magnesium cations with chloride, sulphate and bicarbonate anions up to a total molality of at least 5 mol·kg−1. The independent variables in this new model are reduced temperature, ion molalities and the mole fraction of CO2 dissolved in the aqueous phase. The latter is related to temperature, pressure and ion molalities by an improved model for the mutual solubility. More than 2000 experimental data points were used in the development of the two models. For the IFT of the CO2-H2O binary system, the overall root-mean-square deviation (RMSD) is 0.65mN·m−1 while the absolute average relative deviation (AARD) is 1.8%. In the case of mutual solubility, the RMSD of CO2 mole fraction in the aqueous phase is 0.0003 and the AARD is 5.5% while, in the non-aqueous phase, the RMSD of H2O mole fraction is 0.0035 and the corresponding AARD is 8.7%. Similar results are found for the CO2-brine systems.

Rice husk derived biogenic silica coated cotton as an effective, sustainable oil-water separation platform

Oil-spills present a significant threat to the environmental marine bio-diversity. Conventional cleaning approaches such as skimming are costly. In this regard, alternative approaches utilizing functional nanoparticles (NP) are on the rise due to their effectiveness in separating the non-aqueous phase. This work presents a facile yet sustainable methodology using environmentally-friendly biogenic silica for removing oil from an oil-water mixture. To begin with, an agricultural-waste, rice husk (RH), is subjected to slow pyrolysis under CO2 environment to obtain bio-char. Bio-char is then treated at different pH and calcined, to generate silica NP. Process parameters such as reactor temperature, and pH of biochar-treating solution, are varied to understand their effect on silica NP characteristics. Experiments reveal that pH 5 and temperature 500 °C, facilitate generation of silica NP (∼18 nm). XRD analysis uncovers cristobalite phase presence in NP, which is reported to possess low unit cell volume, thereby contributing to an overall less particle size. Silica NP are modified by treating them with different silanes. PFDS treated silica NP is observed to possess superhydrophobicity, (water contact angle ∼ 160°) and oleophilicity (oil contact angle below 10°). This characteristic is attributed to low surface energy of PFDS. Silica NP coated cotton substrate is then utilized as a sorbent. Repeatability tests reveal that the natural sorbent can effectively separate oil-water mixture even after 40 cycles, with an efficiency of 97%. The findings of this study can aid in development of economical, sustainable platforms for separating oil/water mixtures or harmful components from aqueous/non-aqueous mixture.

Recent Advances in MXene Quantum Dots: A Platform with Unique Properties for General-Purpose Functional Materials with Novel Biomedical Applications.

Developing new, high-performance materials is a prerequisite for technological advancement. In comparison to bulk materials, quantum dots have a number of good advantages due to their small size, high surface area, and quantum dimensions. Quantum dots, two-dimensional materials with lateral dimensions less than 100nm, can be generated by the quantum confinement effect. Mxene quantum dots (MQDs) retain some of their two-dimensional characteristics. They also exhibit novel physicochemical properties, including enhanced dispersibility in aqueous and nonaqueous phases, modification or doping capabilities, and photoluminescence. MQDs, due to their unique and diverse properties, have been receiving a great deal of attention as new members of the Mxene group and wide use for biotechnology, bioimaging, optoelectronics, catalysis, cancer therapy, etc. This review aims to provide an overview of the synthesis of MQDs, their optical properties, and their cancer therapy applications. MQDs exhibit remarkable photothermal and photodynamic features and can be suitable for bioimaging. In addition to obtaining bioimaging, photothermal therapy (PTT) and photodynamic therapy (PDT) effects simultaneously, MQDs have high biocompatibility in vitro and in vivo, providing evidence of their potential clinical utility. Herein, recent developments and future prospects concerning MQDs biomedical applications are discussed.

Pore-scale investigation of surfactant-enhanced DNAPL mobilization and solubilization

Surfactant-enhanced aquifer remediation has been proved successful to remove dense non-aqueous phase liquids (DNAPLs) from contaminated sites. However, the underlying mechanisms of the DNAPL mobilization and solubilization at the pore scale remains to be addressed for efficient application to the field remediation system. In this work, the emerging microfluidic and imaging technologies are applied to investigate the dynamics of DNAPL remediation. Visualized experiments of the evolution of DNAPL remediation are performed to study the role of surfactant type, concentration and injection rate. The DNAPL remediation is dominated by mobilization followed by solubilization for most surfactants. Mobilization occurs as soon as surfactants and DNAPL are in contact until forming a new stable phase structure, and the solubilization continues until the end of injection. We observe the breakup behavior of long droplets and ganglia during the mobilization, which is attributed to the surfactant-reduced interfacial tension and thus expedites DNAPL mobilization and redistribution. During the solubilization, the formation of micelles incorporating DNAPL fractions increases the DNAPL concentration gradient and thus enhances the mass transfer, but the rate-limited diffusion of micelles reduces the mass transfer rate coefficient. Increasing the surfactant content and decreasing the injection rate can promote mobilization and solubilization. The DNAPL mobilization ability of the surfactants SDS and SDBS is stronger than SAOS and Tween 80 regardless of the injection rates. Tween 80 may be considered an ideal surfactant of only solubilization but not mobilization is desired. This work elucidates the pore-scale mechanisms during surfactant-enhanced DNAPL remediation, which are beneficial for upscaling studies, predictive modeling, and operation optimization of DNAPL remediation in the field.

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.

Remediation of multilayer soils contaminated by heavy chlorinated solvents using biopolymer-surfactant mixtures: Two-dimensional flow experiments and simulations.

To assess the efficiency of remediating dense non-aqueous phase liquids (DNAPLs), here heavy chlorinated solvents, through injection of xanthan solutions with or without surfactant (sodium dodecylbenzenesulfonate: SDBS), we conducted a comprehensive investigation involving rheological measurements, column (1D) and two-dimensional (2D) sandbox experiments, as well as numerical simulations on two-layers sand packs. Sand packs with grain sizes of 0.2-0.3mm and 0.4-0.6mm, chosen to represent the low and high permeable soil layers respectively, were selected to be representative of real polluted field. The rheological analysis of xanthan solutions showed that the addition of SDBS to the solution reduced its viscosity due to repulsive electrostatic forces and hydrophobic interactions between the molecules while preserving its shear-thinning behavior. Results of two-phase flow experimentsdepicted that adding SDBS to the polymer solution led to a reduced differential pressure along the soil and improvements of the DNAPL recovery factor of approximately 0.15 and 0.07 in 1D homogeneous and 2D layered systems, respectively. 2D experiments revealed that the displacement of DNAPL in multilayer zones was affected by permeability difference and density contrast in a heterogeneous soil. Simulation of multiphase flow in a multilayered system was performed by incorporating non-Newtonian properties and coupling the continuity equation with generalized Darcy's law. The results of modeling and experiments are very consistent. Numerical simulations showed that for an unconfined soil, the recovery of DNAPL by injection of xanthan solution can be reduced for more than 50%. In a large 2D experimental system, the combination of injecting xanthan with blocking the contaminated zone led to a promising remediation of DNAPL-contaminated layered zones, with a recovery of 0.87.

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.

The Effects of Spill Pressure on the Migration and Remediation of Dense Non-Aqueous Phase Liquids in Homogeneous and Heterogeneous Aquifers

The spill pressure of the contaminant source is an important factor affecting the amount, location, form, and behavior of the dense non-aqueous phase liquids (DNAPLs) that plume in a contaminated subsurface environment. In this study, perchloroethylene (PCE) infiltration, distribution and, remediation via a surfactant-enhanced aquifer remediation (SEAR) technique for a PCE spill event are simulated to evaluate the effects of the spill pressure of the contaminant source on the DNAPLs’ behavior in two-dimensional homogeneous and heterogeneous aquifers. Five scenarios with different spill pressures of contamination sources are considered to perform the simulations. The results indicate that the spill pressure of the contaminant source has an obvious influence on the distribution of DNAPLs and the associated efficiency of remediation in homogeneous and heterogeneous aquifers. As the spill pressure increases, more and more contaminants come into the aquifer and the spread range of contamination becomes wider and wider. Simultaneously, the remediation efficiency of contamination also decreases from 93.49% to 65.90% as the spill pressure increases from 33.0 kPa to 41.0 kPa for a heterogeneous aquifer with 200 realizations. The simulation results in both homogeneous and heterogeneous aquifers show the same influence of the spill pressure of the contaminant source on PCE behaviors in the two-dimensional model. This study indicates that the consideration of the spill pressure of the contaminant sources (such as underground petrol tanks, underground oil storage, underground pipeline, and landfill leakage) is essential for the disposal of contaminant leakage in the subsurface environment. Otherwise, it is impossible to accurately predict the migration and distribution of DNAPLs and determine the efficient scheme for the removal of contaminant spills in groundwater systems.

Lipase as Biocatalyst- for Synthesis of Phenol by Using Box–Behnken Design

This work highlighted the proficient and naturally safe methodology for the phenol synthesis using biocatalyst lipase. The development of sustainable synthetic protocol for various organic transformations is an important area of research attracts researchers to avoid use of volatile and hazardous organic solvents in reaction for greener and eco-friendly protocols. Lipase is subclass of esterase enzymes and acts as biocatalyst with industrial significance. They carry out biochemical transformation in non-aqueous and aqueous phases quickly. To further make the process more specific Design Expert software was used for the optimization of synthesize phenol for maximum % Yield and % Purity. Effect of temperature, Concentration of Catalyst, and Volume of Water was selected as an independent factor to get the maximum % Yield and % Purity of the phenol. The results confirmed the mathematical model robustness and justify experimental design. Therefore, the current protocol for synthesis of phenols from phenylboronic acid is greenest and environmentally benign alternative. The current convention has many benefits, like phenomenal product yields, reduced time of reaction, simple procedure to work up, and extensive substrate scope, cost-effective and also lipase was recuperated and reused multiple times without significant loss of its catalytic activity.

Experimental investigation on post-combustion CO2 capture for [Bpy][NO3] and MEA aqueous blends with lower regeneration energy

CO2 capture is an important technology to achieve carbon emission reduction. The key is reducing the energy consumption of the CO2 capture process. Ionic liquids (ILs) blended with organic amines can be used as an efficient CO2 absorbent allowing for low regeneration energy consumption. This work proposes the use of N-butylpyridinium nitrate ([Bpy][NO3]) in combination with organic solvents for CO2 capture. The effects of ILs concentration, reboiler load and flue gas concentration on regeneration energy consumption were studied on a continuous pilot unit for absorption-desorption process. The results showed that the CO2 absorption capacity of 30 wt% MEA + 10 wt% [Bpy][NO3] was 0.1308 g CO2/g solvent, higher than monoethanolamine/water, and the CO2 absorption capacity remained at 74.3% after the five cycles. At 40 °C, the viscosity of IL-amine blending solvents before and after absorption was 2.01 and 3.534 mPa·s, respectively, significantly lower than that of the conventional non-aqueous phase absorbent. The continuous absorption-desorption results showed that the capture rate of IL blending reached more than 95%. The regeneration energy consumption is 34.2% lower than the 30 wt% MEA.

Representative Elementary Volume Estimation and Neural Network-Based Prediction of Change Rates of Dense Non-Aqueous Phase Liquid Saturation and Dense Non-Aqueous Phase Liquid–Water Interfacial Area in Porous Media

Investigation of the change rate for contaminant parameters is important to characterize dense non-aqueous phase liquid (DNAPL) transport and distribution in groundwater systems. In this study, four experiments of perchloroethylene (PCE) migration are conducted in two-dimensional (2D) sandboxes to characterize change rates of PCE saturation (So) and PCE–water interfacial area (AOW) under different conditions of salinity, surface active agent, and heterogeneity. Associated representative elementary volume (REV) of the change rate of So (So rate) and change rate of AOW (AOW rate) is derived over the long-term transport process through light transmission techniques. REV of So rate (SR-REV) and REV of AOW rate (AR-REV) are estimated based on the relative gradient error (εgi). Regression analysis is applied to investigate the regularity, and a model based on a back-propagation (BP) neural network is built to simulate and predict the frequencies of SR-REV and AR-REV. Experimental results indicated the salinity, surface active agent, and heterogeneity are important factors that affect the So rate, AOW rate, SR-REV, and AR-REV of the PCE plume in porous media. The first moment of the PCE plume along the vertical direction is decreased under conditions of high salinity, surface active agent, and heterogeneity, while these factors have different effects on the second moment of the PCE plume. Compared with the salinity and surface active agent, heterogeneity has the greatest effect on the GTP, the distributions of the So rate and AOW rate along the depth, and dM, dI. For SR-REV, the standard deviation is increased by the salinity, surface active agent, and heterogeneity. Simultaneously, the salinity and heterogeneity lead to lower values of the mean value of SR-REV, while the surface active agent increases the mean value of SR-REV. However, the mean and standard deviation of AR-REV have no apparent difference under different experimental conditions. These findings reveal the complexity of PCE transport and scale effect in the groundwater system, which have important significance in improving our understanding of DNAPL transport regularity and promoting associated prediction.

Enhanced mass transfer of residual NAPL by convection in stagnant zone

Cosolvent flushing is a promising method to improve NAPLs (non-aqueous phase liquids) removal. Nevertheless, the removal performance is undermined by the tailing phenomenon, i.e., the contaminant concentration tends to remain unchanged in later period as NAPL is residually trapped in the stagnant zone. High proportion of stagnant zone leads to more severe tailing phenomenon and how to accelerate dissolution of NAPL in the stagnant zone is important for NAPL remediation. However, few work has studied the remediation process at pore-scale due to limited observation techniques. As a result, the fundamental process of convection enhancement remains unclear. In this work, dynamics of NAPL removal in the stagnant zone is quantitatively investigated in transparent micromodels via the use of Raman spectroscopy. Impacts of injection condition and properties of the porous media are systematically investigated. Results indicate that convection dominants the mass transfer in aqueous phase and enhances the NAPL dissolution. Increasing the flushing velocity can enhance convection, but when the flushing velocity exceeds 3 cm/min, convection in the region away from the dominant channel is little affected by the flushing velocity. Differently, increasing the pore throat size will enhance convection in the entire stagnant zone and accelerate the whole dissolution process.

Numerical investigations of influence on thermal conductive heating in DNAPL-impacted soils by heterogeneity

The treatment of dense non-aqueous phase liquid (DNAPL) source zones is challenging, particularly in heterogeneous media. Thermal conductive heating (TCH) has the potential to treat DNAPL source zones for its ability to enhance mass transfer. This study uses numerical modeling combined with Monte Carlo simulation to examine the influence of heterogeneity of the permeability field on the DNAPL distribution and TCH remediation. It is found that the longer horizontal correlation length of high-permeable clay lens would contribute to accelerate multiphase convection and then heat conduction in horizontal direction. The presence of DNAPL (both in NAPL phase and dissolved), pressure, and permeability are all contributory factors to phase change. Realizations with shorter horizontal correlation lengths always have a larger vertical spreading of DNAPL. As a shallow vapor extraction well was applied in this study, higher TCE removal rate can be obtained in the realizations with a shorter horizontal correlation length when NAPL phase of TCE is existed in the domain.

Increased styrene vapor removal and power production by adding silicone oil to microbial fuel cell-based trickling filter

This study increases the mass transfer of hydrophobic contaminants in a microbial fuel cell-based trickling filter (MFC/TF) by adding non-aqueous phase liquid. The removal efficiency, mineralization efficiency and elimination capacity of styrene are respectively increased by 1.56 times, 1.86 times and 1.52 times, the power density is increased by 2.6 times and the internal resistance is reduced by approximately 22% after adding 10% silicone oil to the MFC/TF. This is mainly attributed to a decrease in the internal resistance after adding silicone oil, which increases electron transfer on the surface of the auxiliary anode packing and increases the number of electricity-producing bacteria. Adding 10% silicone oil to the MFC/TF increases the number of degrading bacteria and electricity-generating bacteria in the MFC/TF by 2.3–2.5 times. The performance of the MFC/TF using 10% silicone oil is significantly increased because there is increased mass transfer of styrene in the MFC/TF and increased power generation.

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.

Experimental upscaling analyses for a surfactant-enhanced in-situ chemical oxidation (S-ISCO) remediation design

Surfactant-enhanced in-situ chemical oxidation (S-ISCO) is an emerging innovative remediation technology for the treatment of dense non-aqueous phase liquids (DNAPLs). S-ISCO combines the solubilization of contaminants by means of surfactants with the chemical oxidation by an oxidizing agent, thus, potentially increasing the efficiency of the state-of-the-art ISCO technique. Scientific investigations are needed to enable the technology transfer for potential field applications based on the development of a remediation design under well-defined boundary conditions.For this purpose, experimental upscaling analyses were performed using the special infrastructure of the research facility for subsurface remediation (VEGAS). Batch tests showed that oxidation of the selected surfactant E-Mulse 3® (EM3) by activated persulfate (Na-PS) reduced the solubilization of the model contaminants 1,4-DCB, naphthalene, and PCE. As a consequence, the processes of contaminant solubilization and degradation were temporally and spatially separated in the developed remediation design.A proof of concept was provided by performing an S-ISCO medium-scale experiment (100 cm length, 70 cm height, 12.5 cm width), with 1,2-DCB as model DNAPL contaminant to be treated. A groundwater circulation well (GCW) was used to inject a 60 g/L Na-PS solution and to effectively mix the reagents. Sampling of the experiment's outflow and the soil material after treatment showed that neither rebound effects nor residual mass loadings on the soil material could be detected after termination of the S-ISCO treatment.To further evaluate the S-ISCO remediation design under field-like conditions, a large-scale S-ISCO experiment was conducted (6 m length, 3 m height, 1 m width), allowing for an extensive sampling campaign to monitor relevant processes. An efficient contaminant removal from the former source zone could be reached by surfactant solubilization, decreasing contaminant levels from initially over 2000 mg/L 1,2-DCB to final concentrations below 5 mg/L 1,2-DCB. The heterogeneously distributed contaminant degradation, implemented by a three-filter GCW, was attributed to density-induced migration processes that impeded an optimal reaction zone. A density-dependent numerical transport could qualitatively match the observations. By comparing different simulation scenarios, an adapted operation of the GCW was established that provides for a more efficient distribution of the density-influenced oxidant injection.

Bayesian ensemble machine learning-assisted deterministic and stochastic groundwater DNAPL source inversion with a homotopy-based progressive search mechanism

A hyperheuristic homotopy algorithm (HH-HA) and a homotopy-based swarm intelligence algorithm for parallel stochastic search are proposed to improve the search ergodicity and stability of deterministic and stochastic inversion approaches, respectively, for the identification of dense nonaqueous phase liquid (DNAPL) source characteristics and contaminant transport parameters in groundwater. Meanwhile, a Bayesian ensemble machine learning (BEML) method for numerical simulation surrogate modeling is proposed to enhance the learning and generalization capability, while significantly reducing the computational cost of repetitive CPU-demanding likelihood evaluations in inversion iterations. Two cases are presented for the verification and application of the proposed inverse modeling methods. The results show that the BEML surrogate model is powerful in approximating the numerical model outputs, reducing the mean relative errors of the contaminant concentration and pressure head predictions to 1.18% and 1.29%, respectively. The homotopy-based progressive search mechanism is highly effective in achieving more accurate identification values for deterministic inversion and a more reliable posterior distribution for stochastic inversion. The HH-HA shows stable performance, approaching the global optimum in wide areas and reducing the mean relative error of identification from 11.95% to 4.11%. The homotopy-based parallel stochastic search lines adequately cover the search space tracking the change of homotopy parameter, and the mean relative error of point estimation is reduced to 2.03%. Though the deterministic inversion approach can provide intuitive identification values, the reliability of the inversion outputs cannot be quantified. In contrast, the proposed stochastic inversion system is of great significance for providing decision makers with comprehensive reference information.