title: Discovery of 40 Classes of Per- and Polyfluoroalkyl Substances in Historical Aqueous Film-Forming Foams (AFFFs) and AFFF-Impacted Groundwater.
abstract: 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.
authors.affiliation: Department of Chemistry, Oregon State University , 153 Gilbert Hall, Corvallis, Oregon 97331, United States.
authors.forename: Krista A
authors.identifier: 0000-0002-9330-4569
authors.initials: KA
authors.lastname: Barzen-Hanson
authors.affiliation: Department of Civil and Environmental Engineering, Colorado School of Mines , 1500 Illinois St., Golden, Colorado 80401, United States.
authors.forename: Simon C
authors.initials: SC
authors.lastname: Roberts
authors.affiliation: Nicholas School of the Environment, Duke University , Durham, North Carolina 27708, United States.
authors.forename: Sarah
authors.initials: S
authors.lastname: Choyke
authors.affiliation: Department of Civil and Environmental Engineering, Colorado School of Mines , 1500 Illinois St., Golden, Colorado 80401, United States.
authors.forename: Karl
authors.initials: K
authors.lastname: Oetjen
authors.affiliation: Wellington Laboratories Inc., 345 Southgate Drive, Guelph, Ontario, Canada N1G 3M5.
authors.forename: Alan
authors.initials: A
authors.lastname: McAlees
authors.affiliation: Wellington Laboratories Inc., 345 Southgate Drive, Guelph, Ontario, Canada N1G 3M5.
authors.forename: Nicole
authors.initials: N
authors.lastname: Riddell
authors.affiliation: Department of Chemistry, University of Guelph , Guelph, Ontario, Canada N1G 2W1.
authors.forename: Robert
authors.initials: R
authors.lastname: McCrindle
authors.affiliation: Nicholas School of the Environment, Duke University , Durham, North Carolina 27708, United States.
authors.forename: P Lee
authors.initials: PL
authors.lastname: Ferguson
authors.affiliation: Department of Civil and Environmental Engineering, Colorado School of Mines , 1500 Illinois St., Golden, Colorado 80401, United States.
authors.forename: Christopher P
authors.initials: CP
authors.lastname: Higgins
authors.affiliation: Department of Environmental and Molecular Toxicology, Oregon State University , 1007 ALS Building, 2750 SW Campus Way, Corvallis, Oregon 97331, United States.
authors.forename: Jennifer A
authors.initials: JA
authors.lastname: Field
mesh_terms: D002853:Chromatography, Liquid; D005466:Fluorocarbons; D060587:Groundwater / Q000737:chemistry; D014867:Water; D014874:Water Pollutants, Chemical
chemical_list: D005466:Fluorocarbons; D014874:Water Pollutants, Chemical; D014867:Water