PFOS Mass Flux Reduction/Mass Removal: Impacts of a Lower-Permeability Sand Lens within Otherwise Homogeneous Systems.

Perfluorooctane sulfonic acid (PFOS) is one of the most common per- and polyfluoroalkyl substances (PFAS) and is a significant risk driver for these emerging contaminants of concern. A series of two-dimensional flow cell experiments was conducted to investigate the impact of flow field heterogeneity on the transport, attenuation, and mass removal of PFOS. A simplified model heterogeneous system was employed consisting of a lower-permeability fine sand lens placed within a higher-permeability coarse sand matrix. Three nonreactive tracers with different aqueous diffusion coefficients, sodium chloride, pentafluorobenzoic acid, and β-cyclodextrin, were used to characterize the influence of diffusive mass transfer on transport and for comparison to PFOS results. The results confirm that the attenuation and subsequent mass removal of the nonreactive tracers and PFOS were influenced by mass transfer between the hydraulically less accessible zone and the coarser matrix (i.e., back diffusion). A mathematical model was used to simulate flow and transport, with the values for all input parameters determined independently. The model predictions provided good matches to the measured breakthrough curves, as well as to plots of reductions in mass flux as a function of mass removed. These results reveal the importance of molecular diffusion and pore water velocity variability even for systems with relatively minor hydraulic conductivity heterogeneity. The impacts of the diffusive mass transfer limitation were quantified using an empirical function relating reductions in contaminant mass flux (MFR) to mass removal (MR). Multi-step regression was used to quantify the nonlinear, multi-stage MFR/MR behavior observed for the heterogeneous experiments. The MFR/MR function adequately reproduced the measured data, which suggests that the MFR/MR approach can be used to evaluate PFOS removal from heterogeneous media.