Impacts of Environmental and Engineered Processes on the PFAS Fingerprint of Fluorotelomer-Based AFFF

Forensic analysis can potentially be used to determine per- and polyfluoroalkyl substance (PFAS) sources at contaminated sites. However, fluorotelomer aqueous film-forming foam (AFFF) sources are difficult to identify because the polyfluorinated active ingredients do not have authentic standards and because the parent compounds can undergo transformation and differential transport, resulting in alteration of the PFAS distribution or fingerprint. In this study, we investigate changes in the PFAS fingerprint of fluorotelomer-derived AFFF due to environmental and engineered processes, including groundwater transport, surface water flow, and land application of contaminated biosolids. Fingerprint analysis supplemented by quantification of precursors and identification of suspected active ingredients shows a clear correlation between a fluorotelomer AFFF manufacturer and surface water of nearby Lake Michigan, demonstrating contamination (>100 ng/L PFOA) of the lake due to migration of an AFFF-impacted groundwater plume. In contrast, extensive processing during wastewater treatment and environmental transport results in large changes to the AFFF fingerprint near agricultural fields where contaminated biosolids were spread. At biosolids-impacted sites, the presence of active ingredients confirms contamination by fluorotelomer AFFF. While sediments can retain longer-chain PFAS, this study demonstrates that aqueous samples are most relevant for PFAS fingerprinting in complex sites, particularly where shorter-chain compounds have been used.