Mass transfer during surfactant-enhanced DNAPL remediation: Pore-scale experiments and new correlation

Surfactant-enhanced solubilization has been proven successful to remediate aquifers contaminated with non -aqueous phase liquids (DNAPLs). Understanding mass transfer from DNAPLs to the surfactant solution is high-ly important for improving remediation efficiency. However, the pore-scale mechanisms underlying the effect of surfactants on mass transfer behaviors have not been fully understood. Here we use microfluidic experiments to investigate the fundamental physical processes and quantify the impacts of surfactants on mass transfer rate at the pore scale. We find that surfactants can induce droplet breakup behaviors due to the interfacial disparity of mass transfer strength, resulting in the subsequent micro-movement of daughter blobs due to capillary force. Through image-based measurements, we find a significant inhibition of the mass transfer rates by surfactants at concentrations above the critical micelle concentration, and the inhibition becomes more pronounced as the concentration increases, which can be explained by an increase in stagnant film thickness. But the total mass transfer flux is improved because of the enhanced driving force caused by the surfactant-enhanced concentration gradient. In light of the observed physical processes and the behavior of mass transfer inhibition, we finally develop a new empirical model that explicitly considers the effects of surfactant concentration, DNAPL distri-bution, effective interface area, and flow rate to predict the mass transfer rate. This work provides pore-scale underpinnings of the mass transfer behaviors and a new mass transfer model considering the effect of surfac-tants, which improves the understanding of interphase mass transfer processes under the action of surfactants in subsurface hydrological and engineering systems.