Air-water interfacial areas relevant for transport of per and poly-fluoroalkyl substances.

Per and polyfluoroalkyl substances (PFAS) present in the soil pose a long-term threat to groundwater. Robust characterization and modeling of PFAS retention and transport in unsaturated systems requires an accurate determination of the magnitude of air-water interfacial area (AWIA). Multiple methods are available for measuring or estimating air-water interfacial area, including x-ray microtomography (XMT), various aqueous and gas-phase interfacial tracer-test (ITT) methods, and thermodynamic-based estimation methods. AWIAs determined with the different methods can vary significantly. Therefore, it is critical to determine which measurement methods are relevant for application to PFAS retention and transport. This is achieved by employing AWIAs determined with different methods to simulate the results of miscible-displacement experiments reported in the literature for the transport of perfluorooctanoic acid (PFOA) in an unsaturated quartz sand. Measured PFOA breakthrough curves were successfully predicted using AWIA values measured by aqueous ITT methods. Conversely, AWIAs measured with the XMT method and estimated with the thermodynamic method under-predicted the magnitude of retardation and could not successfully simulate the measured transport data. These results indicate that the ITT method appears to provide the most appropriate AWIA values for robust characterization and modeling of PFAS transport in unsaturated systems. The long-term impact of employing different AWIA values on PFOA leaching in the vadose zone was simulated for a representative AFFF application scenario. The predicted timeframes for PFOA migration to groundwater varied from 3 to 6 to 20 years depending on which AWIA was used in the simulation. These relatively large differences would result in significantly different risk-assessment outcomes. These results illustrate that it is critical to employ the AWIA that is most representative of PFAS retention for accurate predictions of PFAS leaching in the vadose zone.