Density modification of DNAPL using self-demulsifying colloidal biliquid aphron: Kinetics, mechanisms and influencing factors.

Density-modification remediation of dense nonaqueous phase liquid (DNAPL) using colloidal biliquid aphron (CBLA) is an efficient means of enhancing flushing and avoiding the risk of downward migration of DNAPL. However, the use of demulsifier is currently necessary for CBLA to achieve density modification. This leads to issues such as low modification efficiency and the risk of secondary contamination. In this work, we developed a self-demulsifying CBLA (PO-CBLA-S) for density-modification remediation of DNAPL, eliminating the need for external demulsifiers. The self-demulsification process exhibited pseudo-secondary reaction kinetics, achieving densities below 1 g/cm for various DNAPLs. Groundwater chemistry parameters (pH, anions, cations, temperature, and humic acid (HA) content) were investigated for their impact on perchloroethylene (PCE) density modification. Cations were found to enhance PO-CBLA-S density modification more than anions. Both strong acidic and alkaline environments promote the density regulation of PCE by PO-CBLA-S, and temperature positively correlates with the efficiency of density modification. High concentrations of HA also have a favorable facilitating effect on the density modification. The mechanisms of self-demulsifying density modification were clarified at the microscale. Surfactant entanglement caused by internal surfactant-solvent interaction decreased the stability of PO-CBLA-S, leading to self-demulsification. This study addresses density modification challenges and provides a theoretical foundation for its groundwater remediation applications.