Pore-Scale Mechanisms of Solid Phase Emergence during DNAPL Remediation by Chemical Oxidation

In situ chemical oxidation (ISCO) has proven successful in the remediation of aquifers contaminated with dense nonaqueous phase liquids (DNAPLs). However, the treatment efficiency can often be hampered by the formation of solids or gas, reducing the contact between remediation agents and residual DNAPLs. To further improve the efficiency of ISCO, fundamental knowledge is needed about the complex multiphase flow and reactive transport processes as new solid and fluid phases emerge at the microscale. Here, via microfluidic experiments, we study the pore-scale dynamics of trichloroethylene degradation by permanganate. We visualize how the remediation evolves under the influence of solid phase emergence and explore the roles of injection rate, oxidant concentration, and stabilization supplement. Combining image processing, pressure analysis, and stoichiometry calculations, we provide comprehensive descriptions of the oxidant concentration-dependent growth patterns of the solid phase and their impact on the remediation efficiency. We further corroborate the stabilization mechanism provided by phosphate supplement, which is effective in inhibiting solid phase generation and thus highly beneficial for the oxidation remediation. This work elucidates the pore-scale mechanisms during remediation of chlorinated solvents with a particular context in the solid phase production and the associated effects, which is of general significance to understanding various processes in natural and engineered systems involving solid phase emergence or aggregation phenomena, such as groundwater and soil remediation.