Hillslope groundwater discharges provide localized stream ecosystem buffers from regional per- and polyfluoroalkyl substances contamination

Emerging groundwater contaminants such as per- and polyfluoroalkyl substances (PFAS) may impact surface-water quality and groundwater-dependent ecosystems of gaining streams. Although complex near-surface hydrogeology of stream corridors challenges sampling efforts, recent advances in heat tracing of discharge zones enable efficient and informed data collection. For this study, we used a combination of streambed temperature push-probe and thermal infrared methods to guide a discharge-zone-oriented sample collection along approximately 6 km of a coastal trout stream on Cape Cod, MA. Eight surface-water locations and discharging groundwater from 24 streambed and bank seepages were analysed for dissolved oxygen (DO), specific conductance, stable water isotopes, and a range of PFAS compounds, which are contaminants of emerging concern in aquatic environments. The results indicate a complex system of groundwater discharge source flowpaths, where the sum of concentrations of six PFAS compounds (corresponding to the U.S. Environmental Protection Agency third Unregulated Contaminant Monitoring Rule "UCMR 3") showed a median concentration of 52 +/- 331 (SD) ng/L with two higher outliers and three discharges with PFAS concentrations below the quantification limit. Higher PFAS concentration was related (-0.66 Spearman rank, p < .001) to discharging groundwater that showed an evaporative signature (deuterium excess), indicating flow through at least one upgradient kettle lake. Therefore, more regional groundwater flowpaths originating from outside the local river corridor tended to show higher PFAS concentrations as evaluated at their respective discharge zones. Conversely, PFAS concentrations were typically low at discharges that did not indicate evaporation and were adjacent to steep hillslopes and, therefore, were classified as locally recharged groundwater. Previous research at this stream found that the native brook trout spawn at discharge points of groundwater recharged on local hillslopes, likely in response to generally higher levels of DO. Our study shows that by targeting high oxygen discharges the trout may thereby be avoiding emerging contaminants such as PFAS in groundwater recharged farther from the stream.