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Environmental distribution and bioaccumulation of understudied PFAS surrounding two fluoropolymer manufacturing sites in Italy and the United States.
Citation:
Robuck, A., S. Valsecchi, J. McCord, M. Strynar, M. Cantwell, M. Cashman, S. Polesello, M. Rusconi, M. Parolini, B. De Felice, AND R. Lohmann. Environmental distribution and bioaccumulation of understudied PFAS surrounding two fluoropolymer manufacturing sites in Italy and the United States. SETAC Europe, Dublin, IRELAND, April 30 - May 04, 2023.
Impact/Purpose:
Per- and polyfluoroalkyl substances (PFAS) that were recently introduced in industry lack rigorous data describing their environmental distribution and potential effects. This study seeks to fill data gaps about an understudied group of PFAS called chloroperfluoropolyether carboxylates or Cl-PFPECAs. We compare and contrast data from two locations subject to Cl-PFPECA exposure; data from both locations are in good agreement and indicate Cl-PFPECAs are environmentally persistent and equally or more bioaccumulative compared to legacy PFAS. This work underscores the continued need to screen for understudied PFAS in different environmental matrices/locations, and may be of interest to regional partners, international stakeholders, and local communities.
Description:
1. Introduction With the phase-out of some per- and polyfluoroalkyl substances (PFAS) like perfluorooctanesulfonic acid (PFOS), replacement PFAS have been introduced in consumer and industrial applications across the globe. Little is known about the occurrence, biological accumulation, or potential impacts of some of these replacement PFAS, even though some of them have been in use for years or decades. Here we used tandem mass spectrometry (MS/MS) and high-resolution mass spectrometry (HRMS) to evaluate emerging PFAS in surface water, sediment, and fish tissue from the Delaware River (USA) and the Bormida River (Italy). These river systems are adjacent to similar fluoropolymer manufacturing activities, with known overlap of specific PFAS processing aids in production at both sites. Previous work in both regions has demonstrated the presence of understudied PFAS incorporating at least one chlorine atom and one or multiple ether linkages, called chloroperfluoropolyether carboxylates, or Cl-PFPECAs [1, 2]. 2. Materials and methods In the Delaware River, samples were collected from 2018-2021. In the Bormida River, samples were collected 2020 – 2022. At both sites, water and sediment samples were collected via grab sampling, while fish were collected and donated by recreational fishermen (USA) or collected as part of monitoring efforts (IT). Environmental samples from Italy were analyzed using targeted methods via tandem mass spectrometry, and six chlorinated ethers were quantified compared to a reference standard provided by industry. Targeted, suspect, and non-targeted analysis were conducted on environmental samples collected in the USA using HRMS and MS/MS; only targeted or suspect results are presented in this presentation. Six chlorinated chemicals were quantified using the same industry-provided reference standard used in Italian analysis while suspect screening was conducted for additional chlorinated, hydrogenated, and fluorinated homologs of Cl-PFPECAs based on accurate mass information and diagnostic fragments. 3. Results and Discussion Environmental samples from both locations demonstrate an abundance of Cl-PFPECAs in surface water, sediment, and fish from the sampling region, with the highest levels observed adjacent to and downstream from each suspected point source, respectively. Surface water concentrations of Cl-PFPECAs were on the same order of magnitude in both locations, with maximum sum concentrations totaling ~1780 ng/L in Italy and ~750 ng/L from the Delaware River in the USA. C6O4, a novel ether-based PFAS, was found abundantly in surface water and fish samples from Italy, with concentrations up to 410 ng/L in river water downstream from the suspected point source. This compound was not apparent in any environmental matrix from the Delaware River. Bioaccumulation factors (BAF) were calculated for ten chlorinated homologs in fish tissue compared to surface water concentrations. BAF estimates from both Italy and the USA were in good agreement, and suggest that the larger molecular weight Cl-PFPECAs demonstrate bioaccumulative behavior equal to or surpassing PFOS (log BAF ≈ 3-4), with calculated logBAFs ranging from approximately 2 – 7. Species, dietary habits, and fish size may contribute to the variability of logBAF observed across both systems. Legacy PFAS including PFNA, PFOS, and PFOA were also identified in surface water and fish tissue from both sites, with some fish muscle concentrations in the Delaware River and the Bormida River fish exceeding human consumption advisories issued by the state of NJ. 4. Conclusions These data from two distinct river systems suggests novel Cl-PFPECAs can distribute readily in environmental matrices proximate to sites known to use or produce these chemicals. Moreover, these data suggest Cl-PFPECAs may be equally or substantially more bioaccumulative compared to legacy PFAS like PFOS or PFNA.
URLs/Downloads:
ABSTRACT-BOOK-FINAL2.PDF (PDF, NA pp, 12556.428 KB, about PDF)https://europe2023.setac.org/
