Dataset Information

Identification of novel fluorochemicals in aqueous film-forming foams used by the US military.

ABSTRACT: Aqueous film-forming foams (AFFFs) are a vital tool to fight large hydrocarbon fires and can be used by public, commercial, and military firefighting organizations. In order to possess these superior firefighting capabilities, AFFFs contain fluorochemical surfactants, of which many of the chemical identities are listed as proprietary. Large-scale controlled (e.g., training activities) and uncontrolled releases of AFFF have resulted in contamination of groundwater. Information on the composition of AFFF formulations is needed to fully define the extent of groundwater contamination, and the first step is to fully define the fluorochemical composition of AFFFs used by the US military. Fast atom bombardment mass spectrometry (FAB-MS) and high resolution quadrupole-time-of-flight mass spectrometry (QTOF-MS) were combined to elucidate chemical formulas for the fluorochemicals in AFFF mixtures, and, along with patent-based information, structures were assigned. Sample collection and analysis was focused on AFFFs that have been designated as certified for US military use. Ten different fluorochemical classes were identified in the seven military-certified AFFF formulations and include anionic, cationic, and zwitterionic surfactants with perfluoroalkyl chain lengths ranging from 4 to 12. The environmental implications are discussed, and research needs are identified.

SUBMITTER: Place BJ

PROVIDER: S-EPMC3390017 | biostudies-literature | 2012 Jul

REPOSITORIES: biostudies-literature

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Identification of novel fluorochemicals in aqueous film-forming foams used by the US military.

Place Benjamin J BJ Field Jennifer A JA

Environmental science & technology 20120615 13

Aqueous film-forming foams (AFFFs) are a vital tool to fight large hydrocarbon fires and can be used by public, commercial, and military firefighting organizations. In order to possess these superior firefighting capabilities, AFFFs contain fluorochemical surfactants, of which many of the chemical identities are listed as proprietary. Large-scale controlled (e.g., training activities) and uncontrolled releases of AFFF have resulted in contamination of groundwater. Information on the composition ...[more]

PMID: 22681548

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Project description:The deployment of aqueous film forming foams (AFFF) used for firefighting during emergencies and training often releases per- and polyfluoroalkyl substances (PFAS) into the environment. In October 2018, first responders in Providence, RI, USA applied an AFFF during a fuel spill. Due to the proximity of the incident to the upper reaches of Narragansett Bay (NB), an unknown quantity of gasoline and AFFF entered the estuary via surface runoff and stormwater drains. Water samples near the spill were collected approximately 15 h after the incident and analyzed for 24 PFAS. Minor increases in measured PFAS concentrations were observed relative to pre- and post-spill samples at monitoring sites near the incident, except 6:2-fluorotelomer sulfonate (6:2-FTS) that peaked post-spill (max 311 ng/L). After performing the total oxidizable precursor (TOP) assay on water samples and the AFFF concentrate, significant increases in perfluorocarboxylic acids (PFCAs) were observed. One compound, 6:2 fluorotelomer mercaptoalkylamido sulfonate (6:2-FTSAS), was identified as a major component of the AFFF used. Peak areas of 6:2-FTSAS and the degradation product 6:2-FTSAS-sulfoxide corresponded to observed increases in the TOP assay results and were useful as tracers of AFFF in surrounding waters. Elevated levels of PFAS at the time of sampling were limited to a confined area of the Providence River due to river flow and tidal action. Observed concentrations were also compared to hydrodynamic model results, and results confirmed rapid dissipation of AFFF components with distance from the spill. However, modeled results did not capture possible secondary releases of AFFF from local municipal stormwater and sewer infrastructure, as observational data suggest. The multiple lines of evidence of PFAS present in surface waters permitted a better assessment of the potential environmental impacts from products such as AFFF for which the chemical composition is largely unknown.

Project description:BackgroundDrinking water contamination related to the use of aqueous film-forming foam (AFFF) has been documented at hundreds of military bases, airports, and firefighter training facilities. AFFF has historically contained high levels of long-chain per- and polyfluoroalkyl substances (PFAS), which pose serious health concerns. However, the composition and toxicity of legacy AFFF mixtures are unknown, presenting great uncertainties in risk assessment and affected communities.ObjectivesThis study aimed to determine the fluorinated and nonfluorinated chemical composition of a legacy AFFF sample and its toxicity in zebrafish embryos.MethodsA sample of legacy AFFF (3% application formulation, manufactured before 2001) was provided by the Massachusetts Department of Environmental Protection. High resolution mass spectrometry (HRMS) was used to identify PFAS and nonfluorinated compounds, and a commercial laboratory measured 24 PFAS by a modified U.S. EPA Method 537.1. AFFF toxicity was assessed in zebrafish embryos in comparison with four major constituents: perfluorooctanesulfonic acid (PFOS); perfluorohexanesulfonic acid (PFHxS); sodium dodecyl sulfate (SDS); and sodium tetradecyl sulfate (TDS). End points included LC50 values, and sublethal effects on growth, yolk utilization, and pancreas and liver development.ResultsWe identified more than 100 PFAS. Of the PFAS detected, PFOS was measured at the highest concentration (9,410mg/L) followed by PFHxS (1,500mg/L). Fourteen nonfluorinated compounds were identified with dodecyl sulfate and tetradecyl sulfate the most abundant at 547.8 and 496.4mg/L, respectively. An LC50 of 7.41×10-4% AFFF was calculated, representing a dilution of the 3% formulation. TDS was the most toxic of the constituents tested but could not predict the AFFF phenotype in larval zebrafish. PFOS exposure recapitulated the reduction in length but could not predict effects on development of the liver, which was the tissue most sensitive to AFFF.DiscussionTo our knowledge, this research is the first characterization of the chemical composition and toxicity of legacy AFFF, which has important implications for regulatory toxicology. https://doi.org/10.1289/EHP6470.

Dataset Information

Identification of novel fluorochemicals in aqueous film-forming foams used by the US military.

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Identification of novel fluorochemicals in aqueous film-forming foams used by the US military.

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