ABSTRACT:

Per- and polyfluoroalkyl substances (PFAS) are surface-active contaminants, which are detected in groundwater globally presenting serious health concerns. The vadose zone and surface water are recognized as primary sources of PFAS contamination. Previous studies have explored PFAS transport and retention mechanisms in the vadose zone, revealing that adsorption at interfaces and soil/sediment heterogeneity significantly influences PFAS retention. However, our understanding of how surface water-groundwater interactions along river corridors impact PFAS transport remains limited. To analyze PFAS transport during surface water-groundwater interactions, we performed saturated-unsaturated flow and reactive transport simulations in heterogeneous riparian sediments. Incorporating uncertainty quantification and sensitivity analysis, we identified key physical and geochemical sediment properties influencing PFAS transport. Our models considered aqueous phase transport and adsorption both at the air-water interface (AWI) and the solid phase surface. We tested different cases of heterogeneous sediments with varying volume proportions of higher permeability sediments, conducting 2,000 simulations for each case, followed by global sensitivity and response surface analyses. Results indicate that sediment porosities, which are correlated to permeabilities, are crucial for PFAS transport in riparian sediments during river stage fluctuations. High permeable sediment (e.g., sandy gravel, sand) is the preferential path for the PFAS transport and the low permeable sediment (e.g., silt, clay) is where PFAS is retained. Additionally, the results show adsorption at interfaces (AWI \& solid phase) have small impact on the PFAS retention in riparian environments. This study offers insights into factors influencing PFAS transport in riparian sediments, potentially aiding the development of strategies to reduce the risk of PFAS contamination in groundwater from surface water.

ABSTRACT:

Hyporheic exchange influences water quality and controls numerous physical, chemical, and biological processes. Despite its importance, hyporheic exchange and the associated dynamics of solute mixing are often difficult to characterize due to spatial (e.g., sedimentary heterogeneity) and temporal (e.g., river stage fluctuation) variabilities. This study coupled geophysical techniques with physical and chemical sediment analyses to map sedimentary architecture and quantify its influence on hyporheic exchange dynamics within a compound bar deposit in a gravel‐dominated river system in southwestern Ohio. Electromagnetic induction (EMI) was used to quantify variability in electrical conductivity within the compound bar. EMI informed locations of electrode placement for time‐lapse electrical resistivity imaging (ERI) surveys, which were used to examine changes in electrical resistivity driven by hyporheic exchange. Both geophysical methods revealed a zone of high electrical conductivity in the centre of the bar, identified as a fine‐grained cross‐bar channel fill. The zone acts as a baffle to flow, evidenced by stable electrical conditions measured by time‐lapse ERI over the study period. Large changes in electrical resistivity throughout the survey period indicate preferential flowpaths through higher permeability sands and gravels. Grain size analyses confirmed sedimentological interpretations of geophysical data. Loss on ignition and x‐ray fluorescence identified zones with higher organic matter content that are locations for potentially enhanced geochemical activity within the cross‐bar channel fill. Differences in the physical and geochemical characteristics of cross‐bar channel fills play an important role in hyporheic flow dynamics and nutrient processing within riverbed sediments. These findings enhance our understanding of the applications of geophysical methods in mapping riverbed heterogeneity and highlight the importance of accurately representing geomorphologic features and heterogeneity when studying hyporheic exchange processes.