Identification of novel polyfluoroalkyl substances in surface water runoff from a chemical stockpile fire

In 2018, over 30,000 L of fluorine-free firefighting foam was used to extinguish an industrial warehouse fire of uncharacterized chemical and industrial waste. Contaminated firewater and runoff were discharged to an adjacent freshwater creek in Melbourne, Australia. In this study, we applied nontarget analysis using liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QToF-MS) to 15 surface water samples to investigate the presence of legacy, novel and emerging per-and polyfluoroalkyl substances (PFAS). We identified six novel and emerging fluorotelomer-based fluorosurfactants in the Australian environment for the first time, including: fluorotelomer sulfonamido betaines (FTABs or FTSA-PrB), fluorotelomer thioether amido sulfonic acids (FTSASs), and fluorotelomer sulfonyl amido sulfonic acids (FTSAS-So). Legacy PFAS including C₆-C₈ perfluoroalkyl sulfonic acids, C₄-C₁₀ perfluoroalkyl carboxylic acids, and perfluoro-4-ethylcyclohexanesulfonate were also detected in surface water. Of note, we report the first environmental detection of ethyl 2-ethenyl-2-fluoro-1-(trifluoromethyl) cyclopropane-1-carboxylate. Analysis of several Class B certified fluorine-free foam formulations allowed for use in Australia revealed that there was no detectable PFAS. Patterns in the homologue profiles of fluorotelomers detected in surface water are consistent with environments impacted by fluorinated aqueous film-forming foams. These results provide strong evidence that firewater runoff of stockpiled fluorinated firefighting foam was the dominant source of detectable PFAS to the surrounding environment.