Novel fluorinated surfactants tentatively identified in firefighters using liquid chromatography quadrupole time-of-flight tandem mass spectrometry and a case-control approach.

Fluorinated surfactant-based aqueous film-forming foams (AFFFs) are made up of per- and polyfluorinated alkyl substances (PFAS) and are used to extinguish fires involving highly flammable liquids. The use of perfluorooctanesulfonic acid (PFOS) and other perfluoroalkyl acids (PFAAs) in some AFFF formulations has been linked to substantial environmental contamination. Recent studies have identified a large number of novel and infrequently reported fluorinated surfactants in different AFFF formulations. In this study, a strategy based on a case-control approach using quadrupole time-of-flight tandem mass spectrometry (QTOF-MS/MS) and advanced statistical methods has been used to extract and identify known and unknown PFAS in human serum associated with AFFF-exposed firefighters. Two target sulfonic acids [PFOS and perfluorohexanesulfonic acid (PFHxS)], three non-target acids [perfluoropentanesulfonic acid (PFPeS), perfluoroheptanesulfonic acid (PFHpS), and perfluorononanesulfonic acid (PFNS)], and four unknown sulfonic acids (Cl-PFOS, ketone-PFOS, ether-PFHxS, and Cl-PFHxS) were exclusively or significantly more frequently detected at higher levels in firefighters compared to controls. The application of this strategy has allowed for identification of previously unreported fluorinated chemicals in a timely and cost-efficient way.

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

[2]  B. Pardo,et al.  The search for alternative aqueous film forming foams (AFFF) with a low environmental impact: physiological and transcriptomic effects of two Forafac(®) fluorosurfactants in turbot. , 2011, Aquatic toxicology.

[3]  Bert van Bavel,et al.  Biotransformation of fluorotelomer compound to perfluorocarboxylates in humans. , 2013, Environment international.

[4]  Jonathan P Benskin,et al.  Biomonitoring of perfluorochemicals and toxicity to the downstream fish community of Etobicoke Creek following deployment of aqueous film-forming foam. , 2010, Aquatic toxicology.

[5]  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.

[6]  Scott A Mabury,et al.  Metabolic products and pathways of fluorotelomer alcohols in isolated rat hepatocytes. , 2005, Chemico-biological interactions.

[7]  P. Hopke,et al.  A targeted/non-targeted screening method for perfluoroalkyl carboxylic acids and sulfonates in whole fish using quadrupole time-of-flight mass spectrometry and MSe , 2014, Analytical and Bioanalytical Chemistry.

[8]  M. Oehme,et al.  Structural identification of isomers present in technical perfluorooctane sulfonate by tandem mass spectrometry. , 2006, Rapid communications in mass spectrometry : RCM.

[9]  Konrad Hungerbühler,et al.  Fluorinated alternatives to long-chain perfluoroalkyl carboxylic acids (PFCAs), perfluoroalkane sulfonic acids (PFSAs) and their potential precursors. , 2013, Environment international.

[10]  Ulf Magnusson,et al.  Perfluoroalkyl acids in subarctic wild male mink (Neovison vison) in relation to age, season and geographical area. , 2013, Environment international.

[11]  Yang Yang,et al.  First report of a Chinese PFOS alternative overlooked for 30 years: its toxicity, persistence, and presence in the environment. , 2013, Environmental science & technology.

[12]  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.

[13]  R. Buck,et al.  Determination of fluorotelomer alcohols by liquid chromatography/tandem mass spectrometry in water. , 2006, Rapid communications in mass spectrometry : RCM.

[14]  M. Stacey,et al.  500. Fluorinated sulphonic acids. Part I. Perfluoro-methane-, -octane-, and -decane-sulphonic acids and their simple derivatives , 1957 .

[15]  R. Letcher,et al.  Highly elevated levels of perfluorooctane sulfonate and other perfluorinated acids found in biota and surface water downstream of an international airport, Hamilton, Ontario, Canada. , 2012, Environment international.

[16]  Nobuyoshi Yamashita,et al.  Trophic magnification of poly- and perfluorinated compounds in a subtropical food web. , 2011, Environmental science & technology.

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

[18]  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.

[19]  A. Seacat,et al.  Biotransformation of N-ethyl-N-(2-hydroxyethyl)perfluorooctanesulfonamide by rat liver microsomes, cytosol, and slices and by expressed rat and human cytochromes P450. , 2004, Chemical research in toxicology.

[20]  Derick R. Peterson,et al.  Plasma phospholipids identify antecedent memory impairment in older adults , 2014, Nature Medicine.

[21]  Jennifer A. Field,et al.  Perfluorinated Surfactants and the Environmental Implications of Their Use in Fire-Fighting Foams , 2000 .

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

[23]  G. Jiang,et al.  Perfluorinated compounds and total and extractable organic fluorine in human blood samples from China. , 2008, Environmental science & technology.

[24]  Ning Wang,et al.  6:2 fluorotelomer sulfonate aerobic biotransformation in activated sludge of waste water treatment plants. , 2011, Chemosphere.

[25]  Kristin Elgh-Dalgren,et al.  Environmental levels and distribution of structural isomers of perfluoroalkyl acids after aqueous fire-fighting foam (AFFF) contamination , 2011 .

[26]  John W. Froehlich,et al.  Half-Life of Serum Elimination of Perfluorooctanesulfonate,Perfluorohexanesulfonate, and Perfluorooctanoate in Retired Fluorochemical Production Workers , 2007, Environmental health perspectives.

[27]  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 .

[28]  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.

[29]  Jeffrey H Mandel,et al.  Epidemiologic Assessment of Worker Serum Perfluorooctanesulfonate (PFOS) and Perfluorooctanoate (PFOA) Concentrations and Medical Surveillance Examinations , 2003, Journal of occupational and environmental medicine.

[30]  Xi-jun Wang,et al.  Metabolomics in diagnosis and biomarker discovery of colorectal cancer. , 2014, Cancer letters.

[31]  J. Field,et al.  Identification of novel fluorochemicals in aqueous film-forming foams used by the US military. , 2012, Environmental science & technology.

[32]  J. Corpart,et al.  Fluorinated surfactants: synthesis, properties, effluent treatment , 2002 .

[33]  S. Mabury,et al.  Bioconcentration of aqueous film-forming foam (AFFF) in juvenile rainbow trout (Oncorhyncus mykiss). , 2013, Environmental science & technology.

[34]  M. Mezcua,et al.  Rapid automated screening, identification and quantification of organic micro-contaminants and their main transformation products in wastewater and river waters using liquid chromatography-quadrupole-time-of-flight mass spectrometry with an accurate-mass database. , 2010, Journal of chromatography. A.

[35]  A. Calafat,et al.  Decline in perfluorooctane sulfonate and perfluorooctanoate serum concentrations in an Australian population from 2002 to 2011. , 2014, Environment international.