ABSTRACT
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. We performed a series of multidimensional experiments considering the displacement of three different tracer plumes (i.e., permanganate, allura red and new coccine) in different background electrolyte solutions. The outcomes of the experiments clearly show that both the compound-specific diffusivity and the charge of the injected and resident ions impact the transport of the selected color tracer plumes, whose evolution was monitored with image analysis. The investigated experimental scenarios led to distinct plume behavior characterized by different mass distribution, average displacement velocities, longitudinal and lateral plume spreading, shape of the invading and receding fronts, as well as dilution of the injected solutes. A numerical simulator, based on the Nernst-Planck-Poisson equations and on aqueous speciation reactions in the pore water, allowed us to quantitatively interpret the experimental results, to capture the observed patterns of plume evolution, and to illuminate the coupling between the governing physico-chemical mechanisms and the controlling role of small scale compound-specific and electrostatic properties. Finally, the model was also extended to a typical configuration of in situ electrokinetic remediation of contaminated groundwater to show the impact of such mechanisms at larger scale.
