Non-Fickian transport processes accelerate the movement of PFOS in unsaturated media: An experimental and modelling study

The transport of per- and polyfluoroalkyl substances (PFASs) through unsaturated source-zone soils is a critical yet poorly understood aspect of their environmental behavior. To date, most experimental studies have only focused on the equilibrium or non-equilibrium partitioning of PFASs to the air-water interface, or solid-phase based equilibrium or non-equilibrium transport. Currently, there are discrepancies between air-water interfacial partitioning (K_ia) results measured using a drainage-based column method (which supports a Langmuir isotherm) when compared to measurements from alternative experimental methods (which support a Freundlich isotherm). We hypothesize that this discrepancy is the result of non-Fickian transport conditions developing during column tests using the drainage method, which reduces the magnitude of the apparent K_ia (K_ia,app) when estimated using the retardation factor correlation from breakthrough curve experiments. To test the validity of this hypothesis, the drainage method was implemented using PFOS in a sand column and compared with prior data collected using a quasi-saturated column method. Results demonstrate that the apparent K_ia was reduced by 3 to 123-fold, resulting in up to 123-fold faster breakthrough of PFOS than predicted with the assumption of equilibrium adsorption to the air-water interface. A novel mobile-immobile model (MIM) of PFAS fate and transport was developed, incorporating a term for anomalously adsorbed solute in the mobile zone to explain highly anomalous data. The modelling results using a modified HYDRUS-1D software show that anomalous air-water interfacial adsorption and/or flowpath channelization are plausible mechanisms for accelerated transport of PFOS and support the application of a Freundlich isotherm for PFOS. Overall, non-Fickian transport mechanisms demonstrate the potential to accelerate PFOS transport through the vadose zone by up to a factor of 123 under specific circumstances. This work demonstrates the assumption of equilibrium adsorption to air-water interfaces, even for homogeneous laboratory experiments, is not necessarily valid.