Determination of organic fluorinated compounds content in complex samples through combustion ion chromatography methods: a way to define a "Total Per- and Polyfluoroalkyl Substances (PFAS)" parameter?

Emerging contaminants are a growing concern for scientists and public authorities. The group of per-polyfluoroalkyl substances (PFAS), known as 'forever chemicals', in complex environmental liquid and solid matrices was analysed in this study. The development of global analytical methods based on combustion ion chromatography (CIC) is expected to provide accurate picture of the overall PFAS contamination level via the determination of extractable organic fluorine (EOF) and adsorbable organic fluorine (AOF). The obtained results may be put into perspective with other methods such as targeted analyses (LC-MS/MS). The impact of pH, the presence of dissolved organic carbon and suspended particles on AOF measurements were explored. The effectiveness of the washing step to remove adsorbed inorganic fluorine (IF) has been proven for samples containing up to 8 mgF.L-1. CIC-based methods showed good repeatability and reproducibility for the complex matrices studied. Environmental applications of these methods have been tested. AOF and EOF analyses could explain between 1 % and 23 % and 0.1 % to 2 % of total organic fluorine (TOF), respectively. The sum of PFAS compounds expressed as fluorine could explain from 0.2 % to 11 % and from 0.003 % to 5 % for AOF and EOF, respectively. These results also suggest that some fluorinated compounds are not adsorbed or extractable and/or lost by volatilisation during the application of AOF and EOF analytical procedure. These findings highlight that AOF and EOF are not entirely efficient as proxy to assess "total PFAS" for assessing environmental contamination by PFAS. However, these methods could still be applied to gain a better understanding of the sources and fate of PFAS in the environment.

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.

Microwave-enhanced thermal removal of organochlorine pesticide (chlordecone) from contaminated soils.

Soil contamination with chlordecone, an organochlorine pesticide, is causing serious health problems, affecting crop production and local livestock valorization in the French West Indies. In-situ chemical reduction (ISCR) processes for soil remediation have shown promise but need improvement in terms of time, cost and effective treatment, particularly for andosol soil types. Our study shows that a 10-min microwave treatment significantly reduces chlordecone concentrations (50-90%) in contaminated andosol and nitisol soils. Dry andosol soils show the highest removal yields and reach a higher final temperature (350 °C). Microwave treatment is in all cases more effective or at least as effective as 60 min of conventional heating at a target temperature of 200 °C. The thermal response of andosol and nitisol to microwave exposure is different, as the former is likely to undergo thermal runaway, reaching high temperatures in a short time, resulting in highly efficient thermal removal of chlordecone. These results encourage further scale-up, particularly for the treatment of andosol soils due to their strong microwave response.

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.

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.

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.

Quantification of biodegradation rate of hydrocarbons in a contaminated aquifer by CO2 δ13C monitoring at ground surface.

Ground surface analysis of CO2 emissions with δ13C determination is experimentally demonstrated to be a potential methodology to monitor, on line, the dynamics of petroleum-hydrocarbon biodegradation in soil aquifers, thanks to the improvement of the Isotopic Ratio Infra Red Spectroscopy technique. Biodegradation rate of remaining hydrocarbon substrates in groundwater can be quantified using basic application of the Rayleigh equations, by δ13CCO2 analysis released at ground surface above the pollution plume instead of usual approaches based on groundwater hydrocarbons δ13C analysis, when physical and chemical properties for the contaminated site meet appropriate conditions. The validation approach for that gasoline contaminated specific site is discussed and verified by comparison of first order attenuation rate constant determined from δ13CCO2 analysis emitted at ground surface and from δ13CTOLUENE analysis in ground water. A kinetic fractionation factor α of 0.9979 (or ε value of -2.1 ± 0.5‰) is estimated for the biodegradation of the most reactive hydrocarbon substrates (TEX). The treatment of this Rayleigh equations by linear regression of δ13CCO2 values along the predominant direction of groundwater flow leads to the following results and conclusions for that site: (i) first order biodegradation rate constants (and annual variation) are maximum after the activation of a Permeable Reactive Barrier (PRB) in May 2014: 0.92(+0.29-0.17) year-1, and during July and October: 0.46(+0.14-0.09) year-1 and minimum in mid-winter in February 2015: 0.17(+0.05-0.03) year-1, given by the estimation range for ε. These results are in the lower range with reported in literature for similar contaminated sites (1.6-18 year-1) considering natural attenuation under sulfate reducing conditions and (ii) the seasonal variation of the first order biodegradation rate constant is mainly correlated with the seasonal variation of the CO2 flux, where maximum values are in summers and minimum values in winters. Both seasonal variations are mainly due to the annual cycle of the natural biodegradation activity at the scale of the pollution plume, rather than the activation of the PRB. This work demonstrates that δ13CCO2 analysis released at ground surface from biodegradation of groundwater hydrocarbons could provide, under characterized and appropriate conditions, a non-intrusive (without soil samplings), fast, and low-cost online method to monitor and therefore to optimize soil remediation processes in real time. (Monitored Natural Attenuation or Enhanced Bioremediation).

Experimental study of DNAPL displacement by a new densified polymer solution and upscaling problems of aqueous polymer flow in porous media.

The remediation of DNAPL-contaminated soil with lower-density fluids is ineffective due to the over-riding of displacing fluid. The densification of biopolymers is experimentally studied to develop a solution with the same density as a pollutant. Polymer solutions and contaminants are characterized through rheometer. A 1D column filled with monodisperse glass beads was used to measure their apparent viscosity in porous media. The displacement of pollutants by biopolymers (such as xanthan gum, guar gum, and carboxymethyl cellulose) and densified solutions based on barite are investigated in the 1D porous column. In addition, the polymer solution flow is studied using an upscaling method based on the shear viscosity measured with rheometer. The upscaling results are compared with the 1D column experimental outcomes. We found that carboxymethyl cellulose is the best for densifying polymer and showed the highest remediation yield for DNAPL remediation. The polymers' rheology was represented well through the Carreau rheological model. The discrepancy of apparent viscosity in porous media from polymers' shear viscosity measured with rheometer is explained by the adsorption of polymers on pore surfaces and deposition of barite particles in a porous medium, which led to a decrease in permeability. The upscaling results are in good agreement with experimental outcomes at low-pressure gradients. The impact of porous media geometry on polymer flow in porous media is described.

Influence of water saturation and soil properties on the removal of organic pollutants using microwave heating.

Properties of fluids and media, such as soil moisture, may play a significant role in the absorption of microwave and heat distribution during the remediation of soil contaminated with volatile and semi-volatile compounds. Previous studies have been performed on soil samples placed inside a microwave oven cavity in a reactor far from the waveguide outlet or directly inside the metal waveguides. These conditions are far from in situ applications where the unsaturated soil is directly exposed to microwaves through the antenna slots. The objective of this study was therefore to understand better how soil temperature and pollutant recovery change during microwave and conduction heating and how soil properties, liquid type, and saturation influence that. We developed a unique experimental setup that consists of a splittable soil column inserted inside the cavity of a modified domestic microwave oven (power 1000 W and frequency 2.45 GHz) so that the soil surface is in direct contact with the radiated microwaves. Experiments with electrical resistance heating using the same column but with a modified design were conducted for comparison. We used three types of soils spanning fine, medium, and coarse sands, and two semi-volatile pollutants (xylene and diesel fuel). The pollutants and water of different volumes (12% and 25%) were mixed with soils to make the artificially contaminated soils. Temperature values were measured at different points along the sand-packed column using fiber-based optical thermocouples. We evaluated treatment efficiency in space (soil analysis) and time (outlet phase decantation). The experimental results show that microwave heating technology is optimal for water saturation of around 12%, which gives the best compromise between the overall dielectric properties and allows rapid and efficient heating. The temperature increases fast at the beginning of the microwave heating and stabilizes because of the latent heat of the water and pollutant vaporization and then increases again but slowly for dry soil conditions. A maximum temperature of 170 °C was achieved after 140 min of microwave heating. The type of soil and pollution can drastically affect remediation efficiency through mechanical mechanisms (because of a pressure increase) in addition to physical mechanisms (evaporation) for pollutant removal. The removal efficiencies, using the outlet fluids decantation, were 67%, 73%, and 75% for fine, medium, and coarse sand, respectively, for the applied heating time. We found that microwave heating works better in coarser sand where classical conduction heating usually failed. Comparing the two types of heating (microwave and conductive heating) under the same conditions highlights that the use of microwaves makes it possible to reach very high temperatures in a shorter time than with thermal conduction heating.

Numerical simulations of high viscosity DNAPL recovery in highly permeable porous media under isothermal and non-isothermal conditions.

We developed a decimetric size model based on coupling generalized Darcy's law and heat-transfer equations to model viscous dense non-aqueous phase liquid (DNAPL) pumping through highly permeable porous media under non-isothermal conditions. The presence of fingering and non-wetting phase ganglia was modeled through an unsteady capillary diffusion coefficient and an arbitrary heterogeneous permeability field. The model was validated using existing experimental data of a simple case, an oil injection in a 2D tank packed with glass beads. Next, we compared the results of this model against a DNAPL extracting situation in the 2D tank to better understand the two-phase flow behavior in highly permeable porous media. We found that natural convection during heating plays an essential role in heat transfer, especially in the wetting phase zone. By adding the dynamic effect (unsteady conditions) we were better able to describe the presence of the ganglia in porous media. We observed good agreement between modeled and experimental oil saturation curves until the breakthrough point, with a mean relative error of about 10% for low and high flow rates, and 8% and 16% after breakthrough for low and high flow rates, respectively. Extracting viscous oil at low flow rates and high temperature generates less fingering and is well described by the generalized Darcy's law. The remobilization of residual non-wetting ganglia after the breakthrough point at the outlet is, however, difficult to simulate using the generalized Darcy's law. In the end, we treated this issue by using a perturbed permeability field to simulate the observed fingering in the 2D tank.

Polycyclic aromatic hydrocarbons remobilization from contaminated porous media by (bio)surfactants washing.

Biosurfactants, surface-active agents produced by microorganisms, are increasingly studied for their potential use in soil remediation processes because they are more environmentally friendly than their chemically produced homologues. In this work, we report on the use of a crude biosurfactant produced by a bacterial consortium isolated from a PAHs-contaminated soil, compared with other (bio)surfactants (Tween80, Sodium dodecyl sulfate - SDS, rhamnolipids mix), to wash PAHs from a contaminated porous media. Assays were done using columns filled with sand or sand-clay mixtures (95:5) spiked with four model PAHs. The crude biosurfactant showed less adsorption to the [sand] and the [sand + clay] columns compared to Tween 80, SDS and the rhamnolipid mix. The biosurfactant showed the second best capacity to remove PAHs from the columns (as dissolved and particulate phases), both from [sand] and [sand + clay], after SDS when applied at lower concentrations than the other sufactants. The effluent concentrations of phenanthrene (PHE), pyrene (PYR) and benzo[a]pyrene (BAP) increased in the presence of the crude biosurfactant. Compared to the control experiment using only water, the global PAHs washed mass (amount of PAHs removed from the columns) increased between 9 and 1000 times for PHE and BAP in the [sand] column, and between 55 and 6000 times respectively for PHE and BAP in the [sand + clay] columns. Moreover, in the [sand + clay] columns, leaching of a part of the clays was observed in the SDS and the biosurfactant injections assays. This clay leaching resulted in higher PAHs removal, due not to desorption but rather to particulate transport. In the context of washing PAH-contaminated soils in biopiles or subsurface remediation, our results could help in sizing the remediation approach using an environmental friendly biosurfactant, before a pump-and-treat process.

Influence of the injection of densified polymer suspension on the efficiency of DNAPL displacement in contaminated saturated soils.

Nowadays the remediation of DNAPL contaminated zones near groundwater has gained great prominence in environmental fields due to the high importance of water resources. In this work, we suggest injecting a densified polymer suspension by adding barite particles to displace DNAPL. To evaluate the efficiency of the densification of polymer suspensions on the displacement of DNAPL, various densities of barite-polymer suspension; lower, equal, and higher than the density of DNAPL were prepared and their rheological behavior was analyzed. Then flow experiments were performed using a decimetric-scale 2D tank. The displacement procedure was monitored with an imaging technique and the production and injection process data were recorded by mass balance interpretation. It was shown that the densification of the polymer suspension could improve the displacement efficiency of DNAPL up to four times. The clogging behavior of barite-polymer suspension was assessed in a 1D column. Generalized Darcy's law and the continuity equation were used to numerically simulate the experimental two-phase flow. To take into account the clogging behavior of the suspension, the transport equation of diluted species was implemented into the model. The simulation results show that the model can properly predicts the experimental consequences.

DNAPL flow and complex electrical resistivity evolution in saturated porous media: A coupled numerical simulation.

Induced Polarization (IP) is a non-intrusive geophysical method to monitor Dense Non-Aqueous Phase Liquid (DNAPL) contamination and remediation processes underground. In this study, an advanced numerical code simulating DNAPL flow and complex electrical resistivity is presented. The model was validated against existing IP results and image measurements that were carried out previously in a series of 2D tank experiment. Multiphase flow modeling in porous media is coupled with electrical current modeling to simulate the process of DNAPL migration and the associated IP response. This brings a broader view of the contamination in space and time compared to surface and borehole measurements, especially when the results are supported by field measurements or laboratory experiments. The simulations are developed in 3D and are performed in COMSOL Multiphysics®. The simulations using petrophysical relationships for in-phase and quadrature resistivity and the results of the experiments are in complete accordance with each other in the parts of the tank where the saturation of DNAPL is relatively low (i.e. especially in the cone of depression in the pumping scenario). However, the parts associated with high saturation of DNAPL show high errors between the in-phase resistivity simulations and the results from experiments. The present work can be regarded as a preliminary study toward further applications of coupled IP-multiphase flow for more accurate detection and monitoring of DNAPLs. It is suggested that the choice of tool/approach in this study be extended to larger-scale studies for further investigation.

Permanganate oxidation of polycyclic aromatic compounds (PAHs and polar PACs): column experiments with DNAPL at residual saturation.

Permanganate is an oxidant usually applied for in situ soil remediation due to its persistence underground. It has already shown great efficiency for dense nonaqueous phase liquid (DNAPL) degradation under batch experiment conditions. In the present study, experimental permanganate oxidation of a DNAPL - coal tar - sampled in the groundwater of a former coking plant was carried out in a glass bead column. Several glass bead columns were spiked with coal tar using the drainage-imbibition method to mimic on-site pollution spread at residual saturation as best as possible. The leaching of organic pollutants was monitored as the columns were flushed by successive sequences: successive injections of hot water, permanganate solution for oxidation, and ambient temperature water, completed by two injections of a tracer before and after oxidation. Sixteen conventional US-EPA PAHs and selected polar PACs were analyzed in the DNAPL remaining in the columns at the end of the experiment and in the particles collected at several steps of the flushing sequences. Permanganate oxidation of the pollutants was rapidly limited by interfacial aging of the DNAPL drops. Moreover, at the applied flow rate chosen to be representative of in situ injections and groundwater velocities, the reaction time was not sufficient to reach high degradation yields but induced the formation and the leaching of oxygenated PACs.

A critical review of the influence of groundwater level fluctuations and temperature on LNAPL contaminations in the context of climate change.

The intergovernmental panel on climate change (IPCC) predicts significant changes in precipitation patterns, an increase in temperature, and groundwater level variations by 2100. These changes are expected to alter light non-aqueous phase liquid (LNAPL) impacts since groundwater level fluctuations and temperature are known to influence both the mobility and release of LNAPL compounds to air and groundwater. Knowledge of these potential effects is currently dispersed in the literature, hindering a clear vision of the processes at play. This review aims to synthesize and discuss the possible effects of the increase in temperature and groundwater level fluctuations on the behavior of LNAPL and its components in a climate change context. In summary, a higher amplitude of groundwater table variations and higher temperatures will probably increase biodegradation processes, the LNAPL mobility, and spreading across the smear zone, favoring the release of LNAPL compounds to the atmosphere and groundwater but decreasing the LNAPL mass and its longevity. Outcomes will, nevertheless, vary greatly across arid, cold, or humid coastal environments, where different effects of climate change are expected. The effects of the climate change factors linked to soil heterogeneities, local conditions, and weathering processes will govern LNAPL behavior and need to be further clarified.

Experimental study of foam propagation and stability in highly permeable porous media under lateral water flow: Diverting groundwater for application to soil remediation.

Foam propagation and stability in highly permeable porous media, encountered in soil pollution applications, are still challenging. Here, we investigated the application of foam for blocking the aquifer to divert the flow from a contaminated zone and, therefore, ease the remediation treatments. The main aim was to better understand the critical parameters when the foam is injected into a highly permeable aquifer with high groundwater flow velocity (up to 10 m/day). A decimetric-scale 2D tank experimental setup filled with 1 mm glass beads was used. The front part of the 2D tank was made of transparent glass to photograph the foam flow using the light-reflected method. The water flow was generated horizontally through injection and pumping points on the sides of the tank. The pre-generated foam was injected at the bottom center of the tank. Water streamlines (using dye tracing) and water saturation were investigated using image interpretation. Results show that 100% of the water flow was diverted during the injection of the foam. Foam stability in porous media depends significantly on the horizontal water flow rate. Recirculating water containing the surfactant increases foam stability. The main mechanism of destruction was identified as the dilution of the surfactant in water. However, the head-loss measurements showed that despite foam destruction, the relative permeability of the water phase in the media remained quite low. Injection of foam increases the radius of gas propagation, thanks to foam's high viscosity, compared to a pure gas injection case. These results are new highlights on the efficiency of foam as a blocking agent, showing that it can also serve as a means for gas transport more efficiently in porous media, especially for soil remediation applications.

Experimental study of thermally enhanced recovery of high-viscosity DNAPL in saturated porous media under non-isothermal conditions.

Thermal enhancement is known to be an efficient way to decrease the residual saturation of some common dense non-aqueous phase liquids (DNAPLs) after pumping. However, the effect of transient heat transfer during the recovery of a high-viscosity contaminant, such as coal tar, in highly permeable porous media is still unknown. A 2D tank experimental setup allowing monitoring of temperature and saturation fields during DNAPL pumping has been developed. Experiments were run under isothermal and non-isothermal conditions, at low and high flow rates. We investigated the presence of viscous fingering and how that influences the shape of the cone of depression, as well as the residual saturation. The saturation fields show that less viscous fingering occurs in pre-heated cases and that heating increases the recovery efficiency. Increasing the temperature increases the critical velocity and the viscosity ratio and helps to stabilize the interface between the non-wetting and wetting phase. Observations were first made on an oil and ethanol fluid pair because its properties were known, before extending the experiments to a coal tar and water fluid pair. Residual oil saturation after pumping was decreased by 6-16% in all pre-heated conditions. Pumping at low flow rate in these conditions leaves the smallest oil residual saturation (20%) after pumping. A low flow rate increases the recovery efficiency by reducing viscous fingering and by spreading the generated heat to a larger part of the tank. Finally, results on coal tar pumping show that the high thermal conductivity of water helps in keeping the temperature high during pumping. The residual coal tar saturation was reduced from 40% at 20 °C to 28% when pre-heating the tank. Operating at a low flow rate and with a uniform temperature is the key to recovering the highest amount of a viscous DNAPL such as coal tar from the soil and satisfying cleanup goals when using thermally enhanced pumping.

Production of biosurfactant using the endemic bacterial community of a PAHs contaminated soil, and its potential use for PAHs remobilization.

Biosurfactants are surface-active agents produced by microorganisms whose use in soil remediation processes is increasingly discussed as a more environmentally friendly alternative than chemically produced surfactants. In this work, we report the production of a biosurfactant by a bacterial community extracted from a polluted soil, mainly impacted by PAHs, in order to use it in a soil-washing process coupled with bioremediation. Nutrient balance was a critical parameter to optimize the production. Best conditions for biosurfactant production were found to be 20 g/L of glucose, 2 g/L of NH4NO3, and 14.2 g/L of Na2HPO4, corresponding to a C/N/P molar ratio equal to 13/1/2. Purification of the produced biosurfactant by acidification and double extraction with dichloromethane as a solvent allowed measuring the Critical Micellar Concentration (CMC) as equal to 42 mg/L. The capacity of the purified biosurfactant to increase the apparent solubility of four reference PAHs (naphthalene, phenanthrene, pyrene and benzo[a]pyrene) was completed. The solubilisation ratios, in mg of PAH/g of biosurfactant for phenanthrene, pyrene and benzo[a]pyrene are 0.214, 0.1204 and 0.0068, respectively. Identification of the bacteria found in the colony producing the biosurfactant showed the presence of bacteria able to produce biosurfactant (Enterobacteriaceae, Pseudomonas), as well as, others able to degrade PAHs (Microbacterium, Pseudomonas, Rhodanobacteraceae).

FerrateVI oxidation of polycyclic aromatic compounds (PAHs and polar PACs) on DNAPL-spiked sand: degradation efficiency and oxygenated by-product formation compared to conventional oxidants.

In situ chemical oxidations are known to remediate PAH contaminations in groundwater and soils. In this study, batch-scale oxidations aim to compare the PAC (polycyclic aromatic compound) degradation of three oxidation processes traditionally applied for soil treatment: permanganate, heat-activated persulfate (60 °C) and Fenton-like activated by magnetite, to results obtained with ferrates (FeVI). Widely studied for water treatments, ferrates are efficient on a wide range of pollutants with the advantage of producing nontoxic ferric sludge after reaction. However, fewer works focus on their action on soil, especially on semi-industrial grade ferrates (compatible with field application). Oxidations were carried out on sand spiked with dense non-aqueous phase liquid (DNAPL) sampled in the groundwater of a former coking plant. Conventional 16 US-EPA PAHs and polar PACs were monitored, especially potential oxygenated by-products that can be more harmful than parent-PAHs. After seven reaction days, only the Fenton-like showed limited degradation. Highest efficiencies were obtained for heat-activated persulfate with no O-PAC ketones formed. Permanganate gave important degradation, but ketones were generated in large amount. The tested ferrates not only gave slightly lower yields due to their auto-decomposition but also induced O-PAC ketone production, suggesting a reactional pathway dominated by oxidoreductive electron transfer, rather than a radical one.