Polyfluorinated Amides as a Historical PFCA Source by Electrochemical Fluorination of Alkyl Sulfonyl Fluorides

2013-01-02T00:00:00Z (GMT) by Derek A. Jackson Scott A. Mabury
Polyfluorinated amides (PFAMs) are a class of compounds produced as byproducts of polyfluorinated sulfonamide synthesis by electrochemical fluorination (ECF). We measured four PFAM derivatives of perfluorooctanoic acid (PFOA) in a wide range of compounds, experimental materials, and commercial products synthesized by ECF. Initial screening was performed using headspace solid phase microextraction gas chromatography mass spectrometry (SPME-GC-MS), and quantification using in-house synthesized standards was accomplished with GC-MS using positive chemical ionization. Two monosubstituted PFAMs, <i>N</i>-methylperfluorooctanamide (MeFOA) and <i>N</i>-ethylperfluorooctanamide (EtFOA), were detected in the majority of materials that were analyzed. Two disubstituted PFAMs, <i>N</i>-methyl-<i>N</i>-(2-hydroxyethyl)­perfluorooctanamide (MeFOAE) and <i>N</i>-ethyl-<i>N</i>-(2-hydroxyethyl)­perfluorooctanamide (EtFOAE), were not detected in any sample, likely because they were never synthesized. The concentrations of PFAMs in the sulfonamide compounds under study ranged from 12 to 6736 μg/g, suggesting their historical importance as PFCA precursors. In each case, branched isomers for PFAMs were detected, providing further support for their link to an ECF source. A hydrolysis study performed at pH 8.5 showed no degradation of EtFOA to PFOA after 8 days due to the stability of the amide bond. The environmental fate of PFAMs is suggested to be volatilization to the atmosphere followed by oxidation by hydroxyl radical with a predicted lifetime of 3–20 days. Subsequent PFAM exposure to biota will likely lead to enzymatic hydrolysis of the amide linkage to give a PFCA. Human exposure to PFAMs may have contributed to the presence of branched PFOA isomers in blood by serving as an indirect source. The decline in PFOA concentrations in human blood is consistent with a significant drop in PFAM production concurrent with the POSF phase-out in 2000–2001.