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.

[1]  D. Sedlak,et al.  Persistence of perfluoroalkyl acid precursors in AFFF-impacted groundwater and soil. , 2013, Environmental science & technology.

[2]  Jonathan W. Martin,et al.  Discovery of C5-C17 poly- and perfluoroalkyl substances in water by in-line SPE-HPLC-Orbitrap with in-source fragmentation flagging. , 2015, Analytical chemistry.

[3]  A. Laskin,et al.  Higher-order mass defect analysis for mass spectra of complex organic mixtures. , 2011, Analytical chemistry.

[4]  N. Riddell,et al.  Analysis of perfluoroalkyl anion fragmentation pathways for perfluoroalkyl carboxylates and sulfonates during liquid chromatography/tandem mass spectrometry: evidence for fluorine migration prior to secondary and tertiary fragmentation. , 2007, Rapid communications in mass spectrometry : RCM.

[5]  Mark J. Strynar,et al.  Polyfluorinated compounds: past, present, and future. , 2011, Environmental science & technology.

[6]  Morton A Barlaz,et al.  Orthogonal zirconium diol/C18 liquid chromatography-tandem mass spectrometry analysis of poly and perfluoroalkyl substances in landfill leachate. , 2014, Journal of chromatography. A.

[7]  G. Zeng,et al.  Quaternary ammonium compounds (QACs): a review on occurrence, fate and toxicity in the environment. , 2015, The Science of the total environment.

[8]  Will J. Backe,et al.  Evidence of remediation-induced alteration of subsurface poly- and perfluoroalkyl substance distribution at a former firefighter training area. , 2014, Environmental science & technology.

[9]  Zhanyun Wang,et al.  The precautionary principle and chemicals management: The example of perfluoroalkyl acids in groundwater. , 2016, Environment international.

[10]  Christine Spencer,et al.  Detection of a cyclic perfluorinated acid, perfluoroethylcyclohexane sulfonate, in the Great Lakes of North America. , 2011, Environmental science & technology.

[11]  M. A. Mohd,et al.  Perfluorooctanesulfonate and related fluorochemicals in human blood from several countries. , 2004, Environmental science & technology.

[12]  Craig S Criddle,et al.  Aerobic biotransformation and fate of N-ethyl perfluorooctane sulfonamidoethanol (N-EtFOSE) in activated sludge. , 2008, Environmental science & technology.

[13]  Elsie M. Sunderland,et al.  Detection of Poly- and Perfluoroalkyl Substances (PFASs) in U.S. Drinking Water Linked to Industrial Sites, Military Fire Training Areas, and Wastewater Treatment Plants , 2016, Environmental science & technology letters.

[14]  E. Kissa,et al.  Fluorinated Surfactants and Repellents , 2001 .

[15]  Martin Reinhard,et al.  Occurrence and source characterization of perfluorochemicals in an urban watershed. , 2011, Chemosphere.

[16]  R. Letcher,et al.  Monitoring of perfluorinated compounds in aquatic biota: an updated review. , 2011, Environmental science & technology.

[17]  Jennifer A Field,et al.  Quantitative determination of fluorotelomer sulfonates in groundwater by LC MS/MS. , 2004, Environmental science & technology.

[18]  S. Sauvé,et al.  Generation of Perfluoroalkyl Acids from Aerobic Biotransformation of Quaternary Ammonium Polyfluoroalkyl Surfactants. , 2016, Environmental science & technology.

[19]  Helmut Schwarz,et al.  Gas-phase chemistry of collisionally activated ions , 1983 .

[20]  Derek C G Muir,et al.  Biological monitoring of polyfluoroalkyl substances: A review. , 2006, Environmental science & technology.

[21]  B. Chittim,et al.  Mass spectral studies of native and mass-labeled perfluorooctanesulfonamides. , 2007, Rapid communications in mass spectrometry : RCM.

[22]  J. Haftka,et al.  Experimental hydrophobicity parameters of perfluorinated alkylated substances from reversed-phase high-performance liquid chromatography , 2012 .

[23]  M. Eberlin,et al.  Electrospray mass and tandem mass spectrometry identification of ozone oxidation products of amino acids and small peptides , 2000, Journal of the American Society for Mass Spectrometry.

[24]  James Franklin,et al.  Perfluoroalkyl and Polyfluoroalkyl Substances in the Environment: Terminology, Classification, and Origins , 2011, Integrated environmental assessment and management.

[25]  H. Beau.  Demande de brevet d'invention , 2002 .

[26]  Jennifer Zhang,et al.  Investigation of collision-induced dissociations involving odd-electron ion formation under positive electrospray ionization conditions using accurate mass. , 2010, Rapid communications in mass spectrometry : RCM.

[27]  Lakhwinder S Hundal,et al.  Occurrence and fate of perfluorochemicals in soil following the land application of municipal biosolids. , 2011, Environmental science & technology.

[28]  D. Kuehl,et al.  Chromatographic and mass spectral studies of perfluorooctanesulfonate and three perfluorooctanesulfonamides. , 2003, Rapid communications in mass spectrometry : RCM.

[29]  L. Hanssen,et al.  Exposure to per- and polyfluoroalkyl substances through the consumption of fish from lakes affected by aqueous film-forming foam emissions - A combined epidemiological and exposure modeling approach. The SAMINOR 2 Clinical Study. , 2016, Environment international.

[30]  Emma L. Schymanski,et al.  Identifying small molecules via high resolution mass spectrometry: communicating confidence. , 2014, Environmental science & technology.

[31]  Lingjun Li,et al.  Investigation of several unique tandem mass spectrometric fragmentation patterns of NFDEIDR, an orcokinin analog, and its N-terminal dimethylated form. , 2006, Rapid communications in mass spectrometry : RCM.

[32]  Daryl J. McGoldrick,et al.  A New Fluorinated Surfactant Contaminant in Biota: Perfluorobutane Sulfonamide in Several Fish Species. , 2016, Environmental science & technology.

[33]  J. Field,et al.  Discovery and Implications of C2 and C3 Perfluoroalkyl Sulfonates in Aqueous Film-Forming Foams and Groundwater , 2015 .

[34]  June-Soo Park,et al.  Poly- and perfluoroalkyl substances in wastewater: Significance of unknown precursors, manufacturing shifts, and likely AFFF impacts. , 2016, Water research.

[35]  Michael D McClean,et al.  Identification of Biomarkers of Exposure to FTOHs and PAPs in Humans Using a Targeted and Nontargeted Analysis Approach. , 2016, Environmental science & technology.

[36]  D. Knapen,et al.  The structure of the fire fighting foam surfactant Forafac®1157 and its biological and photolytic transformation products. , 2012, Chemosphere.

[37]  Scott A. Mabury,et al.  Identification of novel fluorinated surfactants in aqueous film forming foams and commercial surfactant concentrates. , 2014, Environmental science & technology.

[38]  L. Alvarez-Cohen,et al.  Aerobic Biotransformation of Fluorotelomer Thioether Amido Sulfonate (Lodyne) in AFFF-Amended Microcosms. , 2015, Environmental science & technology.

[39]  T. Knepper,et al.  High Resolution Mass Spectrometry of Polyfluorinated Polyether-Based Formulation , 2015, Journal of The American Society for Mass Spectrometry.

[40]  David Q. Liu,et al.  Fragmentation of aromatic sulfonamides in electrospray ionization mass spectrometry: elimination of SO(2) via rearrangement. , 2008, Journal of mass spectrometry : JMS.

[41]  W. Gebbink,et al.  Perfluoroalkyl Acids (PFAAs) and Selected Precursors in the Baltic Sea Environment: Do Precursors Play a Role in Food Web Accumulation of PFAAs? , 2016, Environmental science & technology.

[42]  Jonathan P Benskin,et al.  Biodegradation of N-ethyl perfluorooctane sulfonamido ethanol (EtFOSE) and EtFOSE-based phosphate diester (SAmPAP diester) in marine sediments. , 2013, Environmental science & technology.

[43]  D. Karlsson,et al.  Analysis of Aqueous Alkanolamines Using Hydrophilic Interaction Liquid Chromatography and Mass Spectrometry , 2013 .

[44]  Jennifer A Field,et al.  Occurrence and persistence of perfluorooctanesulfonate and other perfluorinated surfactants in groundwater at a fire-training area at Wurtsmith Air Force Base, Michigan, USA. , 2003, Journal of environmental monitoring : JEM.

[45]  J. Field,et al.  Correction to Identification of Novel Fluorochemicals in Aqueous Film-Forming Foams Used by the US Military , 2012 .

[46]  J. Washington,et al.  Identification of Unsaturated and 2H Polyfluorocarboxylate Homologous Series and Their Detection in Environmental Samples and as Polymer Degradation Products. , 2015, Environmental science & technology.

[47]  S. Mabury,et al.  Organic fluorine content in aqueous film forming foams (AFFFs) and biodegradation of the foam component 6 : 2 fluorotelomermercaptoalkylamido sulfonate (6 : 2 FTSAS) , 2013 .

[48]  Philip K Hopke,et al.  Comprehensive Emerging Chemical Discovery: Novel Polyfluorinated Compounds in Lake Michigan Trout. , 2016, Environmental science & technology.

[49]  Jennifer A. Field,et al.  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. , 2013, Environmental science & technology.

[50]  A. Ricci,et al.  From the Collisionally Induced Dissociation to the Enzyme-Mediated Reactions: The Electron Flux Within the Lignan Furanic Ring , 2012 .

[51]  Urs Berger,et al.  Levels and trends of poly- and perfluorinated compounds in the arctic environment. , 2010, The Science of the total environment.

[52]  R. L. Tuve,et al.  METHOD OF EXTINGUISHING LIQUID HYDROCARBON FIRES , 2017 .

[53]  Pawel Rostkowski,et al.  Determination of trace levels of total fluorine in water using combustion ion chromatography for fluorine: a mass balance approach to determine individual perfluorinated chemicals in water. , 2007, Journal of chromatography. A.

[54]  Jennifer A. Field,et al.  Determination of perfluorocarboxylates in groundwater impacted by fire-fighting activity , 1999 .

[55]  Brett J. Vanderford,et al.  Treatment of poly- and perfluoroalkyl substances in U.S. full-scale water treatment systems. , 2014, Water research.

[56]  K. Kannan,et al.  Comparison of total fluorine, extractable organic fluorine and perfluorinated compounds in the blood of wild and pefluorooctanoate (PFOA)-exposed rats: evidence for the presence of other organofluorine compounds. , 2009, Analytica chimica acta.

[57]  S. Mabury,et al.  A North American and global survey of perfluoroalkyl substances in surface soils: Distribution patterns and mode of occurrence. , 2016, Chemosphere.

[58]  Scott A. Mabury,et al.  Using mass defect plots as a discovery tool to identify novel fluoropolymer thermal decomposition products. , 2014, Journal of mass spectrometry : JMS.

[59]  Pawel Rostkowski,et al.  Trace analysis of total fluorine in human blood using combustion ion chromatography for fluorine: a mass balance approach for the determination of known and unknown organofluorine compounds. , 2007, Journal of chromatography. A.

[60]  P. Eklund,et al.  Identification of lignans by liquid chromatography-electrospray ionization ion-trap mass spectrometry. , 2007, Journal of mass spectrometry : JMS.

[61]  G. Langley,et al.  Fragmentation pathways of sulphonamides under electrospray tandem mass spectrometric conditions. , 2003, Rapid communications in mass spectrometry : RCM.

[62]  F. McLafferty.  Interpretation of Mass Spectra , 1966 .

[63]  F. McLafferty.  Unimolecular decompositions of even-electron ions† , 1980 .

[64]  Imma Ferrer,et al.  Identification of Novel Perfluoroalkyl Ether Carboxylic Acids (PFECAs) and Sulfonic Acids (PFESAs) in Natural Waters Using Accurate Mass Time-of-Flight Mass Spectrometry (TOFMS). , 2015, Environmental science & technology.

[65]  U. Siebert,et al.  Temporal trends of polyfluoroalkyl compounds in harbor seals (Phoca vitulina) from the German Bight, 1999-2008. , 2009, Chemosphere.

[66]  Xavier Dauchy,et al.  Mass flows and fate of per- and polyfluoroalkyl substances (PFASs) in the wastewater treatment plant of a fluorochemical manufacturing facility. , 2017, The Science of the total environment.

[67]  Shaily Mahendra,et al.  Biotransformation of 6:2 fluorotelomer alcohol (6:2 FTOH) by a wood-rotting fungus. , 2014, Environmental science & technology.

[68]  Anna Kärrman,et al.  Novel fluorinated surfactants tentatively identified in firefighters using liquid chromatography quadrupole time-of-flight tandem mass spectrometry and a case-control approach. , 2015, Environmental science & technology.

[69]  J. Shabanowitz,et al.  Analysis of organics in the environment by functional group using a triple quadrupole mass spectrometer , 1983 .

[70]  K. Tomer,et al.  Fast atom bombardment and tandem mass spectrometry for characterizing fluoroalkanesulfonates , 1985 .

[71]  E. Beerendonk,et al.  Impact of treatment processes on the removal of perfluoroalkyl acids from the drinking water production chain. , 2012, Environmental science & technology.

[72]  M. Rezende,et al.  Electrospray ionization tandem mass spectrometry analysis of isopimarane diterpenes from Velloziaceae. , 2016, Rapid Communications in Mass Spectrometry.

[73]  S. Mabury,et al.  Are humans exposed to increasing amounts of unidentified organofluorine , 2016 .

[74]  Xiaolin Li,et al.  Quaternary ammonium compounds in urban estuarine sediment environments--a class of contaminants in need of increased attention? , 2010, Environmental science & technology.

[75]  Ning Wang,et al.  8-2 fluorotelomer alcohol aerobic soil biodegradation: pathways, metabolites, and metabolite yields. , 2009, Chemosphere.

[76]  R. V. van Breemen,et al.  High‐performance liquid chromatography–electrospray mass spectrometry of retinoids , 1996, FASEB journal : official publication of the Federation of American Societies for Experimental Biology.

[77]  Fred W. McLafferty,et al.  Mass Spectrometric Analysis. Molecular Rearrangements , 1959 .