Electrostatic and Chemical Interplay between Air-Water and Mineral-Water Interfaces during PFOS Transport in Unsaturated Porous Media.

Perfluorooctanesulfonate (PFOS) migration from vadose zone sources to groundwater is determined by multiple interfacial retention processes and their dependency on hydrochemistry. This study investigates the impact of air-water and mineral-water interfacial retention on PFOS transport under different hydrochemical conditions to assess their adsorption magnitudes and feedback dynamics as a function of ionic strength. Flow-through experiments were conducted in unsaturated quartz and goethite-coated quartz sands equilibrated with different background electrolyte concentrations to distinguish between air-water and goethite-water interfacial adsorption contributions to PFOS retardation.

Low-temperature Aquifer Thermal Energy Storage combined with in situ bioremediation of chlorinated ethenes: Pilot-scale observations and model-based interpretation.

Microbial reductive dechlorination is a key process in aquifers contaminated with chlorinated ethenes and results in a net mass reduction of organic pollutants. Biodegradation rates in the subsurface are temperature-dependent and may be enhanced by increased groundwater temperatures. This study explores the potential of combining the temperature increase from low-temperature Aquifer Thermal Energy Storage with In Situ Bioremediation (ATES-ISB).

Multicomponent and Surface Charge Effects on PFOS Sorption and Transport in Goethite-Coated Porous Media under Variable Hydrochemical Conditions.

Perfluorooctanesulfonate (PFOS), a toxic anionic perfluorinated surfactant, exhibits variable electrostatic adsorption mechanisms on charge-regulated minerals depending on solution hydrochemistry. This work explores the interplay of multicomponent interactions and surface charge effects on PFOS adsorption to goethite surfaces under flow-through conditions. We conducted a series of column experiments in saturated goethite-coated porous media subjected to dynamic hydrochemical conditions triggered by step changes in the electrolyte concentration of the injected solutions.

Estimation of Effective Fracture Aperture in Glacial Tills by Analysis of Dye Tracer Penetration.

This study advances a methodology to estimate effective apertures of fractures in glacial tills based on dye tracer infiltration tests and numerical simulations. The approach uses the visible penetration depth of the dye tracer along fracture flow paths as primary information to calculate effective fracture apertures. Further data used in the calculation are the dye tracer input concentration and retardation, the duration of the tracer injection, and the hydraulic gradient applied to control the infiltrating water fluxes.

Impact of Variable Water Chemistry on PFOS-Goethite Interactions: Experimental Evidence and Surface Complexation Modeling.

Perfluorooctanesulfonate (PFOS) has become a major concern due to its widespread occurrence in the environment and severe toxic effects. In this study, we investigate PFOS sorption on goethite surfaces under different water chemistry conditions to understand the impact of variable groundwater chemistry. Our investigation is based on multiple lines of evidence, including (i) a series of sorption experiments with varying pH, ionic strength, and PFOS initial concentration, (ii) IR spectroscopy analysis, and (iii) surface complexation modeling.

Temperature-dependent dynamics of electrokinetic conservative and reactive transport in porous media: A model-based analysis.

Electrokinetic techniques employ direct current electric fields to enhance the transport of amendments in low permeability porous media and have been demonstrated effective for in situ remediation of both organic contaminants and heavy metals. The application of electric potential gradients give rise to coupled chemical, hydraulic and electric fluxes, which are at the basis of the main transport mechanisms: electromigration and electroosmosis. Previous research has highlighted the significant impacts of charge interactions and fluid composition, including temperature-dependent properties such as electrolyte conductivity and density, on these transport phenomena.

Evolution of plume geometry, dilution and reactive mixing in porous media under highly transient flow fields at the surface water-groundwater interface.

Highly transient boundary conditions affect mixing of dissolved solutes in groundwater. An example of these transient boundary conditions occurs at the surface water-groundwater interface, where the water level in rivers can change rapidly due to the operation of hydropower plants, leading to a regime known as hydropeaking. Inspired by this phenomenon, this work studies at laboratory scale the effects of fluctuating surface water bodies on solute transport in aquifers.

Electrokinetic delivery of permanganate in clay inclusions for targeted contaminant degradation.

The use of electrokinetics (EK) has great potential to deliver reactants in impervious porous media, thus overcoming some of the challenges in the remediation of contaminants trapped in low-permeability zones. In this work we experimentally investigate electrokinetic transport in heterogeneous porous media consisting of a sandy matrix with a target clay inclusion. We demonstrate the efficient EK-delivery of permanganate in the target clay zone (transport velocity 0.

Linking mixing and flow topology in porous media: An experimental proof.

Transport processes in porous media are controlled by the characteristics of the flow field which are determined by the porous material properties and the boundary conditions of the system. This work provides experimental evidence of the relation between mixing and flow field topology in porous media at the continuum scale. The setup consists of a homogeneously packed quasi-two-dimensional flow-through chamber in which transient flow conditions, dynamically controlled by two external reservoirs, impact the transport of a dissolved tracer.

Oxidative Dissolution of Arsenic-Bearing Sulfide Minerals in Groundwater: Impact of Hydrochemical and Hydrodynamic Conditions on Arsenic Release and Surface Evolution.

The dissolution of sulfide minerals can lead to hazardous arsenic levels in groundwater. This study investigates the oxidative dissolution of natural As-bearing sulfide minerals and the related release of arsenic under flow-through conditions. Column experiments were performed using reactive As-bearing sulfide minerals (arsenopyrite and löllingite) embedded in a sandy matrix and injecting oxic solutions into the initially anoxic porous media to trigger the mineral dissolution.

Surface complexation reactions in sandy porous media: Effects of incomplete mixing and mass-transfer limitations in flow-through systems.

Although mixing and surface complexation reactions are key processes for solute transport in porous media, their coupling has not been extensively investigated. In this work, we study the impact of mass-transfer limitations on heterogeneous reactions taking place at the solid-solution interface of a natural sandy porous medium under advection-dominated flow-through conditions. A comprehensive set of 36 column experiments with different grain sizes (0.

On the interplay between electromigration and electroosmosis during electrokinetic transport in heterogeneous porous media.

Electrokinetic techniques represent a valuable approach to enhance solute transport, reactant delivery and contaminant degradation in complex environmental matrices, such as contaminated soil and groundwater, and have a great potential for the remediation of many organic and inorganic pollutants. This study investigates the complex interplay between the key electrokinetic transport mechanisms, electromigration and electroosmosis, in physically heterogeneous porous media and its impact on tracer distribution, reactant mixing and degradation efficiency. We perform experiments in a multidimensional setup, considering different types of heterogeneities, injected tracers and reactants, as well as background electrolyte pore water with different chemical composition and pH.

Impact of solute charge and diffusion coefficient on electromigration and mixing in porous media.

The application of electrokinetic techniques in porous media has great potential to enhance mass transfer rates and, thus, to mobilize contaminants and effectively deliver reactants and amendments. However, the transport mechanisms induced by the application of an external electric field are complex and entail the coupling of physical, chemical and electrostatic processes. In this study we focus on electromigration and we provide experimental evidence of the impact of compound-specific properties, such as the aqueous diffusivity and the valence of charged species, on the macroscopic electrokinetic transport.

Toward a more sustainable mining future with electrokinetic in situ leaching.

Metals are currently almost exclusively extracted from their ore via physical excavation. This energy-intensive process dictates that metal mining remains among the foremost CO emitters and mine waste is the single largest waste form by mass. We propose a new approach, electrokinetic in situ leaching (EK-ISL), and demonstrate its applicability for a Cu-bearing sulfidic porphyry ore.

Impact of diffuse layer processes on contaminant forward and back diffusion in heterogeneous sandy-clayey domains.

Low-permeability aquitards can significantly affect the transport, distribution, and persistence of contaminant plumes in subsurface systems. Although such low-permeability materials are often charged, the key role of charge-induced electrostatic processes during contaminant transport has not been extensively studied. This work presents a detailed investigation exploring the coupled effects of heterogeneous distribution of physical, chemical and electrostatic properties on reactive contaminant transport in field-scale groundwater systems including spatially distributed clay zones.

Arsenic release and transport during oxidative dissolution of spatially-distributed sulfide minerals.

The oxidative dissolution of sulfide minerals, naturally present in the subsurface, is one of the major pathways of arsenic mobilization. This study investigates the release and fate of arsenic from arsenopyrite and löllingite oxidation under dynamic redox conditions. We performed multidimensional flow-through experiments focusing on the impact of chemical heterogeneity on arsenic mobilization and reactive transport.

Electrokinetic Delivery of Reactants: Pore Water Chemistry Controls Transport, Mixing, and Degradation.

Electrokinetics in porous media entails complex transport processes occurring upon the establishment of electric potential gradients, with a wide spectrum of environmental applications ranging from remediation of contaminated sites to biotechnology. The resulting electric forces cause the movement of pore water ions in opposite directions, leading to charge interactions that can affect the distribution of charged species in the domain. Here, we demonstrate that changes in chemical conditions, such as the concentration of a background electrolyte in the pore water of a saturated porous medium, exert a key control on the macroscopic transport of charged tracers and reactants.

Simultaneous determination of stable chlorine and bromine isotopic ratios for bromochlorinated trihalomethanes using GC-qMS.

Bromochlorinated compounds are organic contaminants originating from different natural and anthropic sources and increasingly found in different environmental compartments. This work presents an online approach for compound specific stable isotope analysis of chlorine and bromine isotope ratios for bromochlorinated trihalomethanes using gas chromatography coupled to quadrupole mass spectrometry (GC-qMS). An evaluation scheme was developed to simultaneously determine stable chlorine and bromine isotope ratios based on the mass spectral data of two target compounds: dibromochloromethane and dichlorobromomethane.

Plume deformation, mixing, and reaction kinetics: An analysis of interacting helical flows in three-dimensional porous media.

Heterogeneity and macroscopic anisotropy of porous media play an important role for dilution and reaction enhancement of conservative and reactive plumes. In this study, we perform numerical simulations to investigate steady-state flow and transport in three-dimensional heterogeneous porous media. We consider two macroscopic anisotropic inclusions resulting in helical flows with twisting streamlines in a three-dimensional flow-through domain.

Process-based modeling of electrokinetic-enhanced bioremediation of chlorinated ethenes.

This study presents a process-based modeling analysis of electrokinetic-enhanced bioremediation (EK-Bio) to illuminate the complex interactions between physical, electrostatic and biogeochemical processes occurring during the application of this remediation technique. The features of the proposed model include: (i) multidimensional electrokinetic transport in saturated porous media by electromigration and electroosmosis, (ii) charge interactions, (iii) degradation kinetics, (iv) microbial populations dynamics of indigenous and specialized exogenous degraders, (v) mass transfer limitations, and (vi) geochemical reactions. A scenario modeling investigation is presented, which was inspired by an EK-Bio pilot application conducted in a clayey aquitard at the Skuldelev site (Denmark) contaminated by chlorinated ethenes.

Model-based interpretation of methane oxidation and respiration processes in landfill biocovers: 3-D simulation of laboratory and pilot experiments.

Landfill biocovers are an efficient strategy for the mitigation of greenhouse gas emissions from landfills. A complex interplay between key physical and reactive processes occurs in biocovers and affects the transport of gas components. Therefore, numerical models can greatly help the understanding of these systems, their design and optimal operation.

Impact of iron- and/or sulfate-reduction on a cis-1,2-dichloroethene and vinyl chloride respiring bacterial consortium: experiments and model-based interpretation.

Process understanding of microbial communities containing organohalide-respiring bacteria (OHRB) is important for effective bioremediation of chlorinated ethenes. The impact of iron and sulfate reduction on cis-1,2-dichloroethene (cDCE) and vinyl chloride (VC) dechlorination by a consortium containing the OHRB Dehalococcoides spp. was investigated using multiphase batch experiments.

Charge interactions, reaction kinetics and dimensionality effects on electrokinetic remediation: A model-based analysis.

The potential of electrokinetic remediation technologies (EKR) for the removal of different contaminants from subsurface porous media has been increasingly recognized. Despite electrokinetic applications have shown promising results, quantitative understanding of such systems is still challenging due to the complex interplay between physical transport processes, electrostatic interactions, and geochemical reactions. In this study, we perform a model-based analysis of electrokinetic transport in saturated porous media.

A modeling approach integrating microbial activity, mass transfer, and geochemical processes to interpret biological assays: An example for PCE degradation in a multi-phase batch setup.

The rate at which organic contaminants can be degraded in aquatic environments is not only dependent upon specific degrading bacteria, but also upon the composition of the microbial community, mass transfer of the contaminant, and abiotic processes that occur in the environment. In this study, we present three-phase batch experiments of tetrachloroethene (PCE) degradation by a consortium of organohalide-respiring bacteria, cultivated alone or in communities with iron- and/or sulfate-reducers. We developed a modeling approach to quantitatively evaluate the experimental results, comprised of chemical and biomolecular time series data.

Model-Based Interpretation of Groundwater Arsenic Mobility during in Situ Reductive Transformation of Ferrihydrite.

Arsenic (As) release and mobility in groundwater is coupled to the iron (Fe) cycling and the associated transformation of Fe-oxides present in sediments. Recent in situ experiments have provided observations on arsenic mobilization and co-occurring reductive mineral transformation when placing As-loaded ferrihydrite-coated sand for 80 days in wells of an As-contaminated aquifer of Northern China. However, the complex temporal change in solid-associated arsenic and the multiple geochemical processes occurring when the flowing groundwater contacts the As-loaded ferrihydrite-coated sand hamper a detailed evaluation of the experimental data set.