Surfactant foam injection for remediation of diesel-contaminated soil: A comprehensive study on the role of co-surfactant in foaming formulation enhancement.

Aqueous foam injection is a promising technique for in-situ remediation of soil and aquifers contaminated by petroleum products. However, the application efficiency is strongly hindered by foam's instability upon contact with hydrocarbons. Addressing this, we propose a new binary surfactant mixture of Sodium Dodecyl Sulfate (SDS) and Cocamidopropyl Hydroxysultaine (CAHS). This study investigates CAHS's role as a co-surfactant in enhancing foam stability against antifoaming diesel oil under static and dynamic conditions. Using a dynamic foam analyzer (DFA-100), we assessed static foam's stability by monitoring decay profiles and bubble growth over time. The results revealed that the highest stability can be reached at a CAHS to SDS ratio of 50:50, increasing the half-life of the foam by 7.7 times. Remarkably, our analyses at bulk and bubble scales also elucidated the mechanisms behind the enhanced foam stability of the proposed binary surfactant mixture in the absence and presence of diesel. Additionally, in a 1D sand column, the SDS-CAHS mixture demonstrated more than twofold improvement of the Resistance Factor, attributed to the better survival of the lamellae due to the reduced rate of their destruction. This formulation also yielded a recovery improvement of >10 % compared to SDS foam. The significant improvements in stability and performance of the SDS-CAHS (50:50) mixture were credited to a robust pseudo-emulsion film formation, creating a higher oil entry barrier. This reinforcement and the surfactant molecules' synergistic interactions at the gas-liquid-oil interface significantly contributed to the overall effectiveness.

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.

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.

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 0.2-0.3 mm and 0.4-0.6 mm, 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 experiments depicted 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.

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

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