Exploring the integrity of targeted PFASs in extracted wastewater samples during transport and storage stages

Little information exists on the effects of shipping and handling on per- and polyfluoroalkyl substances (PFASs) in environmental samples. Thus, we evaluated the integrity of dried wastewater extracts and the sensitivity of our high-resolution mass spectrometry (HRMS) instrument to perform such analyses by monitoring 13 representative PFASs in samples extracted, evaporated, and stored at room temperature up to one month. Relative to zero-day recoveries of six detected PFASs ranged between 94 and 124% (RSD <38%) for influents, between 88 and 126% (RSD <18%) for effluents after 28 days. Larger variabilities are tentatively associated with the lack of specific mass-labeled standards and the interactions between analytes and remaining matrix components over time. In a second stage, a mix of local and international dry-shipped wastewater samples were analyzed and the same PFASs were quantified. Up to six PFASs were identified, with median concentrations ranging from 1.3 (perfluoro butyl sulfonate (PFBS)) to 7.7 ng/L (perfluoro hexanoic acid (PFHxA)) and from 1.5 (PFBS) to 13.8 ng/L (PFHxA) in local influents and effluents respectively; and from 0.7 (perfluoro hexyl sulfonate (PFHxS)) to 52.8 ng/L (PFHxA) and from 0.5 (PFHxS) to 21.4 ng/L (PFHxA) in Greek influents and effluents, respectively. The importance of this study lies on the need to consider the wider recovery shifts and expanded variability ranges of PFASs derived from the transport and storage times of dried extracts, particularly when applied to HRMS and wide-scope screening approaches.