Science Inventory

Analysis of Legacy and Novel Neutral Per- and Polyfluoroalkyl Substances in Soils from an Industrial Manufacturing Facility

Citation:

Henderson, W., M. Evich, J. Washington, T. Ward, B. Schumacher, J. Zimmerman, Y. Kim, E. Weber, A. Williams, M. Smeltz, AND D. Glinski. Analysis of Legacy and Novel Neutral Per- and Polyfluoroalkyl Substances in Soils from an Industrial Manufacturing Facility. ENVIRONMENTAL SCIENCE & TECHNOLOGY. American Chemical Society, Washington, DC, 58(24):10729–10739, (2024). https://doi.org/10.1021/acs.est.3c10268

Impact/Purpose:

In the current study, soils obtained from a collaboration with a fluorotelomer-based polymer manufacturing facility in New Jersey, USA were subjected to both targeted and non-targeted analysis of PFCA precursors. Surface soil samples were screened for twenty-two volatile PFAS precursors using GC-positive chemical ionization (PCI)-MS (targeted) including eight nFTOHs, four secondary FTOHs (sFTOHs), six FT-acrylates (FT-Acrs) and four FT-acetates (Table S1) as well as the concentrations of their terminal transformation products (i.e., PFCAs, n=16) determined by LC-MS/MS. Targeted analysis confirmed the presence of these series, specifically the nFTOHs, and non-targeted analysis highlighted additional known and novel industrial manufacturing by-products likely unintentionally produced during the FT-polymerization process.

Description:

Per- and polyfluoroalkyl substances (PFASs) have been detected in an array of environmental media due to their ubiquitous use in industrial and consumer products as well as potential release from fluorochemical manufacturing facilities. During their manufacture, many fluorotelomer (FT) facilities rely on neutral intermediates in polymer production including the FT-alcohols (FTOHs). These PFAS are known to transform to the terminal acids (perfluoro carboxylic acids; PFCAs) at rates that vary with environmental conditions. In the current study on soils from a FT facility, we employed gas chromatography coupled with conventional- and high-resolution mass spectrometry (GC-MS and GC-HRMS) to investigate the profile of these precursor compounds, the intermediary secondary alcohols (sFTOHs), FT-acrylates (FTAcr), and FT-acetates (FTAce) in soils around the former FT-production facility. Of these precursors, the general trend in detection intensity was [FTOHs] > [sFTOHs] > [FTAcrs], while for the FTOHs, homologue intensities generally were [12:2 FTOH] > [14:2 FTOH] > [16:2 FTOH] > [10:2 FTOH] > [18:2 FTOH] > [20:2 FTOH] > [8:2 FTOH] ∼ [6:2 FTOH]. The corresponding terminal acids were also detected in all soil samples and positively correlated with the precursor concentrations. GC-HRMS confirmed the presence of industrial manufacturing byproducts such as FT-ethers and FT-esters and aided in the tentative identification of previously unreported dimers and other compounds. The application of GC-HRMS to the measurement and identification of precursor PFAS is in its infancy, but the methodologies described here will help refine its use in tentatively identifying these compounds in the environment.