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      Identifying and Managing Aqueous Film‐Forming Foam‐Derived Per‐ and Polyfluoroalkyl Substances in the Environment

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          Abstract

          The use of aqueous film‐forming foam (AFFF) has resulted in the widespread occurrence of per‐ and polyfluoroalkyl substances (PFAS) in groundwater, drinking water, soils, sediments, and receiving waters throughout the United States and other countries. We present the research and development efforts to date by the Strategic Environmental Research and Development Program (SERDP) and the Environmental Security Technology Certification Program (ESTCP) to measure PFAS in the environment, characterize AFFF‐associated sources of PFAS, understand PFAS fate and behavior in the environment, assess the risk to ecological receptors, develop in situ and ex situ treatment technologies for groundwater, treat soils and investigation‐derived wastes, and examine the ecotoxicity of PFAS‐free fire suppression formulations. Environ Toxicol Chem 2021;40:24–36. © 2020 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC. This article has been contributed to by US Government employees and their work is in the public domain in the USA.

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          Perfluoroalkyl and Polyfluoroalkyl Substances in the Environment: Terminology, Classification, and Origins

          The primary aim of this article is to provide an overview of perfluoroalkyl and polyfluoroalkyl substances (PFASs) detected in the environment, wildlife, and humans, and recommend clear, specific, and descriptive terminology, names, and acronyms for PFASs. The overarching objective is to unify and harmonize communication on PFASs by offering terminology for use by the global scientific, regulatory, and industrial communities. A particular emphasis is placed on long-chain perfluoroalkyl acids, substances related to the long-chain perfluoroalkyl acids, and substances intended as alternatives to the use of the long-chain perfluoroalkyl acids or their precursors. First, we define PFASs, classify them into various families, and recommend a pragmatic set of common names and acronyms for both the families and their individual members. Terminology related to fluorinated polymers is an important aspect of our classification. Second, we provide a brief description of the 2 main production processes, electrochemical fluorination and telomerization, used for introducing perfluoroalkyl moieties into organic compounds, and we specify the types of byproducts (isomers and homologues) likely to arise in these processes. Third, we show how the principal families of PFASs are interrelated as industrial, environmental, or metabolic precursors or transformation products of one another. We pay particular attention to those PFASs that have the potential to be converted, by abiotic or biotic environmental processes or by human metabolism, into long-chain perfluoroalkyl carboxylic or sulfonic acids, which are currently the focus of regulatory action. The Supplemental Data lists 42 families and subfamilies of PFASs and 268 selected individual compounds, providing recommended names and acronyms, and structural formulas, as well as Chemical Abstracts Service registry numbers. Integr Environ Assess Manag 2011;7:513–541. © 2011 SETAC
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            Discovery of 40 Classes of Per- and Polyfluoroalkyl Substances in Historical Aqueous Film-Forming Foams (AFFFs) and AFFF-Impacted Groundwater.

            Aqueous film-forming foams (AFFFs), containing per- and polyfluoroalkyl substances (PFASs), are released into the environment during response to fire-related emergencies. Repeated historical applications of AFFF at military sites were a result of fire-fighter training exercises and equipment testing. Recent data on AFFF-impacted groundwater indicates that ∼25% of the PFASs remain unidentified. In an attempt to close the mass balance, a systematic evaluation of 3M and fluorotelomer-based AFFFs, commercial products, and AFFF-impacted groundwaters from 15 U.S. military bases was conducted to identify the remaining PFASs. Liquid chromatography quadrupole time-of-flight mass spectrometry was used for compound discovery. Nontarget analysis utilized Kendrick mass defect plots and a "nontarget" R script. Suspect screening compared masses with those of previously reported PFASs. Forty classes of novel anionic, zwitterionic, and cationic PFASs were discovered, and an additional 17 previously reported classes were observed for the first time in AFFF and/or AFFF-impacted groundwater. All 57 classes received an acronym and IUPAC-like name derived from collective author knowledge. Thirty-four of the 40 newly identified PFAS classes derive from electrochemical fluorination (ECF) processes, most of which have the same base structure. Of the newly discovered PFASs found only in AFFF-impacted groundwater, 11 of the 13 classes are ECF-derived, and the remaining two classes are fluorotelomer-derived, which suggests that both ECF- and fluorotelomer-based PFASs are persistent in the environment.
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              Identification of Novel Fluorinated Surfactants in Aqueous Film Forming Foams and Commercial Surfactant Concentrates

              Recent studies comparing the results of total organofluorine-combustion ion chromatography (TOF-CIC) to targeted analysis of perfluoroalkyl and polyfluoroalkyl substances (PFASs) by liquid chromatography tandem mass spectrometry (LC-MS/MS) have shown that a significant yet variable portion of the total organofluorine in environmental and biological samples is in the form of unknown PFASs. A portion of this unknown organofluorine likely originates in proprietary fluorinated surfactants not included in LC-MS/MS analyses and not fully characterized by the environmental science community, which may enter the environment through use in aqueous film forming foams (AFFFs) for firefighting. Contamination of water, biota, and soils with various PFASs due to AFFF deployment has been documented. Ten fluorinated AFFF concentrates, 9 of which were obtained from fire sites in Ontario, Canada, and two commercial fluorinated surfactant concentrates were characterized in order to identify novel fluorinated surfactants. Mixed-mode ion exchange solid phase extraction (SPE) fractionated fluorinated surfactants based on ionic character. High resolution mass spectrometry assigned molecular formulas to fluorinated surfactant ions, while collision induced dissociation (CID) spectra assisted structural elucidation. LC-MS/MS detected isomers and low abundance fluorinated chain lengths. In total, 12 novel and 10 infrequently reported PFAS classes were identified in fluorinated chain lengths from C3 to C15 for a total of 103 compounds. Further research should examine the environmental fate and toxicology of these PFASs, especially their potential as perfluoroalkyl acid (PFAA) precursors.
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                Author and article information

                Contributors
                leeson.andrea@gmail.com
                Journal
                Environ Toxicol Chem
                Environ Toxicol Chem
                10.1002/(ISSN)1552-8618
                ETC
                Environmental Toxicology and Chemistry
                John Wiley and Sons Inc. (Hoboken )
                0730-7268
                1552-8618
                09 December 2020
                January 2021
                : 40
                : 1 ( doiID: 10.1002/etc.v40.1 )
                : 24-36
                Affiliations
                [ 1 ] Strategic Environmental Research and Development Program and the Environmental Security Technology Certification Program Arlington Virginia USA
                [ 2 ] Science and Engineering for the Environment Seattle Washington USA
                [ 3 ] Stroo Consulting Ashland Oregon USA
                [ 4 ] Air Force Civil Engineering Center San Antonio Texas USA
                [ 5 ] Naval Facilities Engineering Command Atlantic, US Navy Philadelphia Pennsylvania USA
                [ 6 ] Office of Research and Development, US Environmental Protection Agency, Office of Research and Development, Cincinnati Ohio USA
                [ 7 ] Naval Sea Systems Command, US Navy Goose Creek South Carolina USA
                [ 8 ] Huntsville Engineering and Support Center, US Army Corps of Engineers Omaha Nebraska USA
                [ 9 ] Alcoa Pittsburgh Pennsylvania USA
                [ 10 ] Independent Consultant Camarillo California USA
                [ 11 ] Noblis Chicago Illinois USA
                Author notes
                [*] [* ]Address correspondence to leeson.andrea@ 123456gmail.com

                Article
                ETC4894
                10.1002/etc.4894
                7839684
                33026660
                91a31998-b685-4e84-a6f0-b57e08562ab0
                © 2020 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC. This article has been contributed to by US Government employees and their work is in the public domain in the USA

                This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc-nd/4.0/ License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made.

                History
                : 07 June 2020
                : 23 June 2020
                : 04 October 2020
                Page count
                Figures: 5, Tables: 5, Pages: 13, Words: 7324
                Funding
                Funded by: Strategic Environmental Research and Development Program (SERDP) and the Environmental Security Technology Certification Program (ESTCP)
                Award ID: Program Funded
                Categories
                Special Section:
                Special Section:
                Article
                Custom metadata
                2.0
                January 2021
                Converter:WILEY_ML3GV2_TO_JATSPMC version:5.9.7 mode:remove_FC converted:27.01.2021

                Environmental chemistry
                aqueous film‐forming foam (afff),per‐ and polyfluoroalkyl substances (pfas),environmental toxicology,analytical chemistry,fate and transport

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