Leaching of Perfluoroalkyl Acids during Unsaturated Zone Flushing at a Field Site Impacted with Aqueous Film Forming Foam.

While several studies have focused on perfluoroalkyl acid (PFAA) leaching from soils, field studies evaluating the relationship between PFAA mass removal and porewater concentrations as the PFAA source becomes depleted are lacking. Herein, in situ water flushing was performed at a site historically impacted with AFFF to accelerate the leaching of PFAAs from unsaturated soils in a highly characterized field test cell. Porous cup suction lysimeters were used to assess the changes in PFAA porewater concentrations as a function of PFAA mass removal from the unsaturated soils, where flushing was intermittently paused to determine ambient PFAA porewater concentrations. Results showed that the fractional decreases in PFAA porewater concentrations during flushing exceeded the fractional decrease in PFAA mass removal from the soil. PFOS porewater concentrations decrease by 76% (with negligible rebound) compared to only a 7.4% decrease in overall PFOS mass removed from the unsaturated zone. Overall, the results observed herein suggest that, when considering soil impacts to groundwater, less stringent soil cleanup criteria than those that consider an equivalent relationship between mass removal and mass discharge may be appropriate. In addition, remedial approaches that remove only a modest fraction of the PFAA soil mass may be protective of underlying groundwater, particularly for perfluorinated sulfonates with at least six carbons.