Zwitterionic, Cationic, and Anionic Fluorinated Chemicals in Aqueous Film Forming Foam Formulations and Groundwater from U.S. Military Bases by Nonaqueous Large-Volume Injection HPLC-MS/MS

Abstract

A new analytical method was developed to quantify 26 newly-identified and 21 legacy (e.g. perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and fluorotelomer sulfonates) per and polyfluorinated alkyl substances (PFAS) in groundwater and aqueous film forming foam (AFFF) formulations. Prior to analysis, AFFF formulations were diluted into methanol and PFAS in groundwater were micro liquid-liquid extracted. Methanolic dilutions of AFFF formulations and groundwater extracts were analyzed by large-volume injection (900 μL) high-performance liquid chromatography tandem mass spectrometry. Orthogonal chromatography was performed using cation exchange (silica) and anion exchange (propylamine) guard columns connected in series to a reverse-phase (C18) analytical column. Method detection limits for PFAS in groundwater ranged from 0.71 ng/L to 67 ng/L, and whole-method accuracy ranged from 96% to 106% for analytes for which matched authentic analytical standards were available. For analytes without authentic analytical standards, whole-method accuracy ranged from 78 % to 144 %, and whole-method precision was less than 15 % relative standard deviation for all analytes. A demonstration of the method on groundwater samples from five military bases revealed eight of the 26 newly-identified PFAS present at concentrations up to 6900 ng/L. The newly-identified PFAS represent a minor fraction of the fluorinated chemicals in groundwater relative to legacy PFAS. The profiles of PFAS in groundwater differ from those found in fluorotelomer- and electrofluorination-based AFFF formulations, which potentially indicates environmental transformation of PFAS.

Per- and polyfluorinated substances (PFASs): Environmental challenges

“…Exposure of human cell lines to 8:2 FTOH and 8:2 mono-and diPAPs decreased androgen and increased estrogen hormone synthesis [231]. PFOS caused A C C E P T E D M A N U S C R I P T ACCEPTED MANUSCRIPT 16 apoptosis of splenocytes and thymocytes and reduction in spleen and thymus weight at high doses [232].…”

“…One serious glitch in the regulation of production and use of long-F-chain PFASs is that companies that did not adhere to the USEPA Stewardship Program immediately started or increased production of these PFASs in order to meet increasing market demands and Multiplication of components in a technical product [16][17][18] also complicates the regulators' task.…”

Methodology for studying biotransformation of polyfluoroalkyl precursors in the environment

“…Moreover, the application of polyfluoroalkyl alternatives with novel functional groups, such as functionalized perfluoropolyethers (PFPEs) and zwitterionic, cationic and anionic fluoroalkyl aqueous film-forming foams, is also increasing [63,64]. New samplepreparation and instrumental methods are in demand to understand the contributions of these polyfluoroalkyl alternatives to PFCAs and PFSAs detected in the environment and biota.…”

Aquatic hazard, bioaccumulation and screening risk assessment for 6:2 fluorotelomer sulfonate

“…Fluorinated surfactants based on fluorotelomer thiol ( (Falk, 1984), e.g., F(CF 2 ) n CH 2 CH 2 SCH 2 CH(OH) CH 2 N + H(CH 3 )CH 2 CO 2 À ) and sulfonyl chemistry ( (Bertocchio and Foulletier, 1971) e.g., F(CF 2 ) n CH 2 CH 2 SO 2 NHCH 2 CH 2 N + (CH 3 ) 2 CH 2 CH 2 CO 2 À ) have also been used in AFFF. As a result of AFFF containing these fluorinated surfactants being used at fire training facilities to control and extinguish major Class B (i.e., flammable, combustible liquids and gases) fires, environmental degradation products such as PFSAs and fluorotelomer sulfonic acids (FTSAs) have been found in ground water and soil (Backe et al, 2013;Houtz et al, 2013). The perfluoroalkane sulfonyl surfactants degrade to the corresponding PFSA, e.g., PFOS, PFHxS, and PFBS (Moody and Field, 2000;Moody et al, 2003;Rhoads et al, 2008).…”