Widespread
concerns have been raised due to the ever-increasing
number of novel per- and polyfluoroalkyl acids (PFAAs) and the ever-decreasing
level of legacy PFAAs. Most analytical methods for PFAAs suffer from
a narrow range of analyzable PFAAs, insufficient sensitivity, poor
performance for oil samples, and defective quantification without
internal standards or blank matrices. To solve these challenges, a
highly selective method for multiple PFAAs from oils and food contact
materials (FCMs) was developed based on nonaqueous electroextraction
(NE). Through theoretical derivation and experimental investigation,
the selectivity of NE was discovered to be tunable, and the range
of extractable analytes could be tuned by adjusting the dielectric
constant of the sample solution. For PFAAs, the selectivity was attributed
to the pK
a-based differential migration
mechanism, as PFAAs exhibited less variable pK
a values in different solvents compared to interference components.
The method achieved nonmatrix-matched calibration without internal
standards and integration of sample cleanup, selective extraction,
and exhaustive enrichment into a fast and convenient operation. The
method provided low limits of detection (0.002–0.03 μg·kg–1), satisfactory accuracy (88.0–107.8%), and
RSDs (<11.7%). Migration experiments from 33 FCMs to oils were
further investigated. PFBS (<0.05–2.34 μg·kg–1) and PFBA (<0.2–0.398 μg·kg–1) were detected from most FCMs. This was the first
attempt at PFAA analysis as well as oil sample analysis using an electric
field-assisted extraction technique and also the first report on PFAA
migration from FCMs into edible oils.