Application of nano-LC-nano-ESI-Orbitrap-MS for trace determination of four priority PFAS in food products considering recently established tolerable weekly intake (TWI) limits

An analytical method was developed and validated for the analysis of four priority perfluoroalkyl substances (PFAS), namely, perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorohexanesulfonic acid (PFHxS), and perfluorooctanesulfonate (PFOS) in food products using nanoscale liquid chromatography (nano -LC) coupled with nanoscale electrospray ionization (nano-ESI) and Orbitrap mass spectrometry (Orbitrap-MS) detection. The efficiency of two different nano-LC setups for chromatographic separation of selected PFAS was evaluated. The optimal LC separation of analytes was achieved using a reversed phase C18 (RP-C18) nano bore column with an integrated emitter. The effect of matrix concentration factor on signal suppression/enhancement was evaluated for different matrices. The method validation indicated analyte recoveries in the range 83-118% and within-laboratory reproducibility from 7 to 18%, while reanalysis of the materials from proficiency tests (PTs) showed that the accuracy of the obtained concentrations ranged from 85 to 124% of the provided consensus values. The method limits of quantification (m-LOQs) were set as first validation levels ranging from 0.001 to 0.3 ng g-1 sample depending on the type of the food group. The observed method performance char-acteristics met the criteria stated in Commission Regulation (EU) 2022/1428, Commission Recommendation (EU) 2022/1431, as well as Guidance Document on Analytical Parameters for the Determination of Per-and Polyfluoroalkyl Substances (PFAS) in Food and Feed with regards to the compliance testing of PFAS maximum levels (MLs) and monitoring purposes. The elaborated method was applied for the analysis of selected priority PFAS in different food groups collected from the Latvian retail market.

Automated summary

An analytical method using nano-LC coupled with nano-ESI and Orbitrap-MS detection was developed and validated for the analysis of four priority PFAS in food products. Two different nano-LC setups were evaluated for chromatographic separation, and the optimal separation was achieved using a RP-C18 nano bore column. The method met the criteria for PFAS compliance testing and monitoring purposes.