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.

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José., Discovery of novel per-and polyfluoroalkyl substances (PFASs) at a fire fighting training ground and preliminary investigation of their fate and mobility, Chemosphere (2017), doi: 10.1016/ j.chemosphere.2017.06.096. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. HIGHLIGHTS: 15• PFASs were investigated at a AFFF impacted fire training ground (FTG) 16• AFFF impacted concrete and soil core samples (0-2m) were analysed by LC-QTOF- 17 MS/MS

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Rapid screening and identification of chemical hazards in surface and drinking water using high resolution mass spectrometry and a case-control filter, Chemosphere (2017), doi: 10.1016/ j.chemosphere.2017.05.071. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. Access to clean, safe drinking water poses a serious challenge to regulators, and requires analytical 18 strategies capable of rapid screening and identification of potentially hazardous chemicals, 19 specifically in situations when threats to water quality or security require rapid investigations and 20 potential response. This study describes a fast and efficient chemical hazard screening strategy for 21 characterising trace levels of polar organic contaminants in water matrices, based on liquid 22 chromatography high resolution mass spectrometry with post-acquisition 'case-control' data 23 processing. This method allowed for a rapid response time of less than 24 hours for the screening of 24 target, suspect and non-target unknown chemicals via direct injection analysis, and a second, more 25 sensitive analysis option requiring sample pre-concentration. The method was validated by fortifying 26 samples with a range of pesticides, pharmaceuticals and personal care products (n=46); with >90% 27 of target compounds positively screened in samples at 1 ng mL -1 , and 46% at 0.1 ng mL -1 when 28 analysed via direct injection. To simulate a contamination event samples were fortified with 29 compounds not present in the commercial library (designated 'non-target compounds'; fipronil and 30 fenitrothion), tentatively identified at 0.2 and 1 ng mL -1 , respectively; and a compound not included 31in any known commercial library or public database (designated 'unknown' compounds; perfluorooctanesulfonic acid), at 0.8 ng mL -1 . The method was applied to two 'real-case' scenarios: 33(1) the assessment of drinking water safety during a high-profile event in Brisbane, Australia; and (2) 34 to screen treated, re-circulated drinking water and pre-treated (raw) water. The validated workflow 35 M A N U S C R I P T A C C E P T E D ACCEPTED MANUSCRIPTwas effective for rapid prioritisation and screening of suspect and non-target potential hazards at 36 trace levels, and could be applied to a wide range of matrices and investigations where comparison 37 of organic contaminants between an affected and control site and or timeframe is warranted. 38 39