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

Rana, Sahil; Marchiandi, Jaye; Partington, Jordan M.; Szabo, Drew; Heffernan, Amy; Symons, Robert; Xie, Shay; Clarke, Bradley O.

doi:10.1016/j.envpol.2022.120055

Cited by 7 publications

(7 citation statements)

References 37 publications

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“…Generally, PFASs exhibit low or negative mass defects due to the replacement of hydrogen (1.0078 Da) atoms in the carbon backbone with fluorine (18.9984 Da). This unique characteristic has been effectively used in workflows to discover novel PFAS in several previous NTA studies. ,, The use of a CF2-normalized mass defect plot (KMD vs m / z ) further facilitates the visualization of prospective PFAS homologues that differ by −CF2– units in complex HRMS feature lists . However, KMD filtering alone was unable to clearly reveal homologous series in these samples, likely due to the complexity of the data acquired from biological samples.…”

Section: Resultsmentioning

confidence: 99%

“…Thus, it should be kept in mind that target PFAS analysis with today’s available reference standards will only detect a fraction of total PFAS at AFFF-contaminated sites. Therefore, non-target analysis (NTA) and suspect screening approaches, which employ HRMS, have been developed over the last decade as complementary analytical techniques to detect a broader range of PFASs in AFFFs − and AFFF-contaminated matrices, , including groundwater, soil, concrete, surface water runoff, and blood serum. − …”

Section: Introductionmentioning

confidence: 99%

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Novel Per- and Polyfluoroalkyl Substances Discovered in Cattle Exposed to AFFF-Impacted Groundwater

Dewapriya,

Nilsson,

Ghorbani Gorji

et al. 2023

Environ. Sci. Technol.

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The leaching of per-and polyfluoroalkyl substances (PFASs) from Australian firefighting training grounds has resulted in extensive contamination of groundwater and nearby farmlands. Humans, farm animals, and wildlife in these areas may have been exposed to complex mixtures of PFASs from aqueous film-forming foams (AFFFs). This study aimed to identify PFAS classes in pooled whole blood (n = 4) and serum (n = 4) from cattle exposed to AFFF-impacted groundwater and potentially discover new PFASs in blood. Thirty PFASs were identified at various levels of confidence (levels 1a−5a), including three novel compounds: (i) perfluorohexanesulfonamido 2-hydroxypropanoic acid (FHxSA-HOPrA), (ii) methyl((perfluorohexyl)sulfonyl)sulfuramidous acid, and (iii) methyl((perfluorooctyl)sulfonyl)sulfuramidous acid, belonging to two different classes. Biotransformation intermediate, perfluorohexanesulfonamido propanoic acid (FHxSA-PrA), hitherto unreported in biological samples, was detected in both whole blood and serum. Furthermore, perfluoroalkyl sulfonamides, including perfluoropropane sulfonamide (FPrSA), perfluorobutane sulfonamide (FBSA), and perfluorohexane sulfonamide (FHxSA) were predominantly detected in whole blood, suggesting that these accumulate in the cell fraction of blood. The suspect screening revealed several fluoroalkyl chain-substituted PFAS. The results suggest that targeting only the major PFASs in the plasma or serum of AFFF-exposed mammals likely underestimates the toxicological risks associated with exposure. Future studies of AFFF-exposed populations should include whole-blood analysis with high-resolution mass spectrometry to understand the true extent of PFAS exposure.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Novel Per- and Polyfluoroalkyl Substances Discovered in Cattle Exposed to AFFF-Impacted Groundwater

Dewapriya,

Nilsson,

Ghorbani Gorji

et al. 2023

Environ. Sci. Technol.

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“…For nontarget screening, three regular rules including homologues series (CF 2 , >3 members), common diagnostic ions (CF 3 , C 2 F 5 , C 3 F 7 , SO 2 F, etc.) and neutral loss (HF and CO 2 ), and Kendrick mass defect (KMD, normalized to CF 2 , <0.15 or >0.85) were used to find potential mass features. For finding homologues series, mass features (S/N > 5, MS response > 2 × 10 5 ) in raw data (Thermo Scientific, USA) were extracted by MS-DIAL, exported in a list including m / z and RT of these features, and then were filtered using an in-house written Python script that screened out the potential ones with specific differences of m / z [e.g., n (CF 2 ) = n *49.9968] and consistent elution order of m / z vs RT.…”

Section: Methodsmentioning

confidence: 99%

Suspect, Nontarget Screening, and Toxicity Prediction of Per- and Polyfluoroalkyl Substances in the Landfill Leachate

Feng,

Lin,

et al. 2024

Environ. Sci. Technol.

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Landfills are the final stage of urban wastes containing perfluoroalkyl and polyfluoroalkyl substances (PFASs). PFASs in the landfill leachate may contaminate the surrounding groundwater. As major environmental pollutants, emerging PFASs have raised global concern. Besides the widely reported legacy PFASs, the distribution and potential toxic effects of numerous emerging PFASs remain unclear, and unknown PFASs still need discovery and characterization. This study proposed a comprehensive method for PFAS screening in leachate samples using suspect and nontarget analysis. A total of 48 PFASs from 10 classes were identified; nine novel PFASs including eight chloroperfluoropolyether carboxylates (Cl-PFPECAs) and bistriflimide (HNTf2) were reported for the first time in the leachate, where Cl-PFPECA-3,1 and Cl-PFPECA-2,2 were first reported in environmental media. Optimized molecular docking models were established for prioritizing the PFASs with potential activity against peroxisome proliferator-activated receptor α and estrogen receptor α. Our results indicated that several emerging PFASs of N-methyl perfluoroalkyl sulfonamido acetic acids (N-MeFASAAs), n:3 fluorotelomer carboxylic acid (n:3 FTCA), and n:2 fluorotelomer sulfonate (n:2 FTSA) have potential health risks that cannot be ignored.

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“…Garcia et al 62 identified eight classes of hydrocarbon surfactants in AFFF-impacted groundwater, suggesting that these substances can persist in anaerobic conditions. Rana et al 66 used nontargeted analysis to identify PFAS in surface water runoff after F3 were used to extinguish a chemical warehouse fire in Australia but did not focus on or identify nonfluorinated surfactants. These findings highlight the need for further research on ensuring the availability of analytical methods and standards for hydrocarbon surfactants in AFFF and F3.…”

Section: Applicationsmentioning

confidence: 99%

Sunrise of PFAS Replacements: A Perspective on Fluorine-Free Foams

Ateia

Buren

Barrett

et al. 2023

ACS Sustainable Chem. Eng.

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One type of firefighting foam, referred to as aqueous film-forming foams (AFFF), is known to contain per- and polyfluoroalkyl substances (PFAS). The concerns raised with PFAS, and their potential environmental and health impacts, have led to a surge in research on fluorine-free alternatives both in the United States and globally. Particularly, in January 2023, a new military specification (MIL-PRF-32725) for fluorine-free foam was released in accordance with Congressional requirements for the U.S. Department of Defense. This paper provides a critical analysis of the present state of the various fluorine-free options that have been developed to date. A nuanced perspective of the challenges and opportunities of more sustainable replacements is explored by examining the performance, cost, and regulatory considerations associated with these fluorine-free alternatives. Ultimately, this evaluation shows that the transition to fluorine-free replacements is likely to be complex and multifaceted, requiring careful consideration of the trade-offs involved. Yet, the ongoing work will provide valuable insights for future research on alternatives to AFFF and enhancing the safety and sustainability of fire suppression systems.

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

Cited by 7 publications

References 37 publications

Novel Per- and Polyfluoroalkyl Substances Discovered in Cattle Exposed to AFFF-Impacted Groundwater

Novel Per- and Polyfluoroalkyl Substances Discovered in Cattle Exposed to AFFF-Impacted Groundwater

Suspect, Nontarget Screening, and Toxicity Prediction of Per- and Polyfluoroalkyl Substances in the Landfill Leachate

Sunrise of PFAS Replacements: A Perspective on Fluorine-Free Foams

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