Insights into PFAS contaminants before and after sewage discharges into a marine protected harbour

Per and polyfluoroalkyl substances (PFAS) and their degradation products are a concern to human and ecosystem health. Wastewater treatment plants are not efficient at removing PFAS compounds and are thought to be a major source of these compounds to marine environments. The sewerage infrastructure in the UK, has over 20,000 combined stormwater overflows (CSOs). These CSOs are relief values whereby untreated wastewater can discharge under permit from the Environment Agency with exceptional rain/snowfall conditions. CSOs discharged 3.6 million monitored hours of untreated wastewater into English rivers and coasts in 2023. Concerns have been raised about the proximity of these CSO discharges to highly protected marine habitats. This study is the first to determine that PFAS concentrations are elevated in a highly protected marine bay (Langstone Harbour, England) following recent sewage releases compared to an extended period without discharge. Analysis was carried out into a suite of 54 PFAS compounds of which only one (PFHpA) was detectable above LOD prior to discharges but 8 afterwards. These included banned PFOS (Linear and Branched 8.6 ng/L ∓ 0.90) and PFOA (2.9 ng/L ∓ 0.29) which were above annual average EQS for inland and 'other' surface waters. Most of the PFAS compounds detected doubled in concentration above LODs. These two-fold increases we discuss are likely conservative estimates based on the use of LODs and tidal conditions. Additional Oysters (Crassostrea gigas) and Seaweed (Fucus vesiculosus) were taken revealing high concentrations of the shorter chain PFBA (6.99μg/kg ∓ 2.42 ww) in seaweed samples. These seaweeds were calculated to have conservative bioaccumulation factors (BAF) > 6000 for PFBA indicating these algae might be an important reservoir of some PFAS contamination. We discuss these results in the context of the largescale discharges of untreated wastewater nationally and globally, and call upon a need for a better understanding of the transfer of PFAS contaminants into marine food chains.