Abstract
Polyfluoroalkyl phosphate mono-, di-, and tri-esters (mono-, di-, and triPAPs) are used to water- and grease-proof food packaging materials, and these chemicals are known precursors to perfluoroalkyl carboxylic acids (PFCAs). Existing analytical methods for PAPs lack sample clean-up steps in the sample preparation. In the present study, a method based on ultra performance liquid chromatography coupled to tandem mass spectrometry (UPLC/MS/MS) was developed and optimized for the analysis of mono-, di-, and triPAPs, including a clean-up step for the raw extracts. The method was applied to food samples and their PAP-containing packaging materials. The optimized UPLC/MS/MS method enabled the separation and identification of a total of 4 monoPAPs, 16 diPAPs, and 7 triPAPs in the technical mixture Zonyl®-RP. For sample clean-up, weak anion exchange solid phase extraction columns were tested. PAPs standard solutions spiked onto the columns were separated into a fraction containing neutral compounds (triPAPs) and a fraction with ionic compounds (mono- and diPAPs) with recoveries between 72–110 %. Method limits of quantification for food samples were in the sub to low picogram per gram range. For quantitative analysis of PAPs, compound-specific labeled internal standards showed to be essential as sorption and matrix effects were observed. Mono-, di-, and/or triPAPs were detected in all food packaging materials obtained from the Swedish market. Up to nine diPAPs were detected in the food samples, with the 6:2/6:2 and 6:2/8:2 diPAPs as the dominant compounds. DiPAP concentrations in the food samples ranged from 0.9 to 36 pg/g, which was comparable to individual PFCA concentrations in the same samples. Consumption of food packed in PAP-containing materials could be an indirect source of human exposure to PFCAs.
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Acknowledgement
This project was funded by the European Union through the PERFOOD project (KBBE-227525). We would like to acknowledge Dr. Tomas Alsberg for his assistance with the UPLC/MS/MS analysis.
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ESM 1
Supplementary material on UPLC/MS/MS parameters, matrix effects, MLOQs, recoveries, PAP patterns in packaging materials and foods, and PFCA detection in packaging materials are provided in Tables S1–S7. Chemical structures of PAPs, MRM chromatograms of coeluting diPAP isomers, a food sample chromatogram, and potential sources of PAPs and PFCAs to food samples are outlined in Figures S1–S4. (DOCX 357 kb)
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Gebbink, W.A., Ullah, S., Sandblom, O. et al. Polyfluoroalkyl phosphate esters and perfluoroalkyl carboxylic acids in target food samples and packaging—method development and screening. Environ Sci Pollut Res 20, 7949–7958 (2013). https://doi.org/10.1007/s11356-013-1596-y
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DOI: https://doi.org/10.1007/s11356-013-1596-y