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. 2012 Jul 3;46(13):7120-7.
doi: 10.1021/es301465n. Epub 2012 Jun 15.

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

Benjamin J Place  1 , Jennifer A Field
Affiliations

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

Benjamin J Place et al. Environ Sci Technol. .

Erratum in

  • Environ Sci Technol. 2012 Oct 2;46(19):10859

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.

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Figures

Figure 1
Figure 1
Timeline of AFFF product addition to the Department of Defense Qualified Products Listing (QPL) that were certified to MIL-F-24385 specifications. While the US military used AFFF since the development in 1963, the records of AFFF on the US military QPL are only available up to 1976. Although 3M remained on the QPL until 2010, the company ceased production of their AFFF product in 2002. “FSP” indicates the AFFF manufacturer Fire Service Plus, Inc.
Figure 2
Figure 2
Workflow scheme for the elucidation of fluorochemical surfactants in AFFF formulations.
Figure 3
Figure 3
Electrofluorination-based fluorinated surfactants identified in AFFF. The perfluoroalkyl chain lengths identified in AFFF are shown as number of n fluorocarbons. The ionic species shown are estimated at an environmentally relevant pH.
Figure 4
Figure 4
Telomerization-based fluorinated surfactants identified in AFFF. The perfluoroalkyl chain lengths identified in AFFF are shown as number of n fluorocarbons. The ionic species shown are estimated at an environmentally relevant pH.
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References

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