Stormwater discharges affect PFAS occurrence, concentrations, and spatial distribution in water and bottom sediment of urban streams

•Stormwater increases PFAS variety and concentrations in streams.•Highest concentrations were measured downstream of urban areas during wet weather.•Stormwater likely transports longer chain PFASs from urban areas to streams.•Sediments near long-standing point sources had higher PFAS concentrations and variety. Per- and polyfluoroalkyl substances (PFAS) are extensively used in urban environments and are, thus, found in urban stormwater. However, the relevance of stormwater as a pathway for PFAS to urban streams is largely unknown. This study evaluated the impact of urban stormwater runoff on PFAS concentrations and spatial distribution in three urban streams affected by stormwater discharges from separate sewer systems. River water was sampled during dry (DW) and wet weather (WW) upstream, immediately downstream, and further downstream of three urbanized areas with separate sewer systems and with and without point sources (i.e. waste water treatment plant, airports). Water samples were analyzed for 34 targeted PFAS compounds and sediment samples for 35 targeted PFAS and 30 PFAS compounds using a total oxidizable precursor assay. The sum of the quantified PFAS concentrations ranged from the reporting limit (RL) to 84.7 ng/L during DW and increased as the streams were affected by WW discharges (0.87 to 102.3 ng/L). The highest PFAS concentrations were found downstream of urban areas and/or point sources (i.e. airports) during WW, indicating a clear contribution from stormwater discharges. A consistent PFAS contribution from the WWTP was observed under both DW and WW conditions. During WW events, concentrations of perfluorooctanesulfonic acid (PFOS) and total PFAS (PFOA equivalents) exceeded the annual average environmental quality standards, which are an established limit of 0.65 ng/L for PFOS and a proposed limit of 4.4 ng/L for total PFAS. Notably, except for the legacy PFAS, PFOS and perfluorooctanoic acid (PFOA), the most frequently quantified PFAS during DW were short-chain. For WW, long-chain perfluorocarboxylic acids (PFCAs) and a precursor, 6:2 Fluorotelomer sulfonic acid (6:2 FTS), were more frequently quantified, suggesting stormwater is a source of these longer-chain and particle-associated PFAS. The detection of unregulated fluorotelomer sulfonates (FTSs) such as 6:2 and 8:2 FTS during WW suggests a need for regulatory action, as these compounds can degrade into more stable PFAS. In sediment, higher concentrations, and a greater variety of PFAS w