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.

A field study to assess the role of air-water interfacial sorption on PFAS leaching in an AFFF source area.

Field-deployed lysimeters were used to measure the concentrations of poly- and perfluoroalkyl substances (PFASs) in soil porewater at a site historically impacted with aqueous film forming foam (AFFF). Samples collected over a 49-day period showed that perfluorooctane sulfonate (PFOS) and perfluorohexane sulfonate (PFHxS) were the PFASs with the highest concentrations in porewater, with concentrations of approximately 10,000 and 25,000 ng L-1, respectively. The corresponding average mass flux to underlying groundwater observed for PFOS and PFHxS was 28,000 ± 11,000 and 92,000 ± 32,000 ng m-2 d-1, respectively. Employing the use of batch desorption isotherms (soil:water slurries) to determine desorption Kd values resulted in an overestimation of PFAS porewater concentrations by a factor for 1.4 to 4. However, using the desorption Kd values from the batch desorption isotherms in combination with a PFAS mass balance that incorporated PFAS sorption at the air-water interface resulted in improved predictions of the PFAS porewater concentrations. This improvement was most notable for PFOS, where inclusion of air-water interfacial sorption resulted in a 58% reduction in the predicted PFOS porewater concentration and predicted PFOS porewater concentrations that were identical (within the 95% confidence interval) to the lysimeter measured PFOS porewater concentration. Overall these results highlight the potentially important role of air-water interfacial sorption on PFAS migration in AFFF-impacted unsaturated soils in an in situ field setting.

Long-term mass flux assessment of a DNAPL source area treated using bioremediation.

This study assessed the long-term effectiveness of bioremediation as a remedial strategy for a chlorinated, ethene dense, non-aqueous phase liquid (DNAPL) source area, consisting of a higher- and a lower-permeability zone at Alameda Point, California. The evaluation was performed over 3.7 years after cessation of active source area bioremediation using passive flux meters (PFMs), push-pull tracer tests, and soil cores. PFMs showed that total chlorinated ethene molar discharge emanating from the source area remained relatively unchanged pre-and post-bioremediation, but molar discharge compositions shifted from trichloroethene (TCE) and cis-1,2-dichloroethene (cis-DCE) to vinyl chloride (VC) and ethene dominated during post-remedial monitoring. First-order rate constants, derived from PFM data at the edge of the source area and describing the complete dechlorination of TCE at 3.7 years following active bioremediation, were approximately 1.05 yr-1, which was over three times lower than the rate 3.6 yr-1 determined using compound stable isotope analysis (CSIA). Soil cores and push-pull tracer test data showed that DNAPL volume estimates were relatively unchanged pre- and post-bioremediation due to the remaining presence of DNAPL in the lower-permeability zone. These data suggest biotransformation processes are continuing in the higher-permeability zone, whereas DNAPL in the lower-permeability zone continues to serve as a significant source of groundwater contamination. The results suggest that it will take many years under current conditions to attain the United States Environmental Protection Agency (EPA) Maximum Contaminant Levels (MCLs) cleanup objectives.

Dense Nonaqueous-Phase Liquid Architecture in Fractured Bedrock: Implications for Treatment and Plume Longevity.

Partitioning tracer testing was performed in discrete intervals within a fractured bedrock tetrachloroethene (PCE) dense nonaqueous-phase liquid (DNAPL) source area to assess the fracture flow field and DNAPL architecture. Results confirmed that the partitioning tracer testing was able to identify and quantify low levels of residual DNAPL along flow paths in hydraulically conductive fractures. DNAPL fracture saturations (Sn) ranged from undetectable to 0.007 (DNAPL volume/fracture volume). A comparison of the fracture flow field to the DNAPL distribution indicated that the highest value of Sn was observed in the least transmissive fracture (or fracture zone). Application of a simple ambient dissolution model showed that the DNAPL present in this low transmissivity zone would persist longer than the DNAPL present in more transmissive fractures and would persist for 200 years (in the absence of any degradation reactions). Assessment of PCE mass distribution between the rock matrix and fractures showed that, due to the presence of DNAPL, the rock matrix accounted for less than 10% of the total PCE mass. The evaluation of PCE concentration profiles in the rock matrix and the estimated diffusional flux from the rock matrix suggest that the elevated PCE groundwater concentrations observed in the fractures likely are due to the presence of the residual DNAPL sources and that removal of the residual DNAPL sources within the fractures would result in a significant decrease in dissolved PCE concentrations in the source area.