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Polyfluoroalkyl phosphate esters and perfluoroalkyl carboxylic acids in target food samples and packaging - method development and screening
Stockholm University, Faculty of Science, Department of Applied Environmental Science (ITM).
Stockholm University, Faculty of Science, Department of Applied Environmental Science (ITM).
Stockholm University, Faculty of Science, Department of Applied Environmental Science (ITM).
Stockholm University, Faculty of Science, Department of Applied Environmental Science (ITM).
2013 (English)In: Environmental Science and Pollution Research, ISSN 0944-1344, E-ISSN 1614-7499, Vol. 20, no 11, p. 7949-7958Article in journal (Refereed) Published
Abstract [en]

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.

Place, publisher, year, edition, pages
2013. Vol. 20, no 11, p. 7949-7958
Keywords [en]
PAPs, FOOD, Precursor, PFCAs, method development, LC-MSMS
National Category
Environmental Sciences
Research subject
Applied Environmental Science
Identifiers
URN: urn:nbn:se:su:diva-93741DOI: 10.1007/s11356-013-1596-yISI: 000325811600040OAI: oai:DiVA.org:su-93741DiVA, id: diva2:648346
Available from: 2013-09-15 Created: 2013-09-15 Last updated: 2022-02-24Bibliographically approved
In thesis
1. Improved analytical methods for perfluoroalkyl acids (PFAAs) and their precursors – a focus on human dietary exposure
Open this publication in new window or tab >>Improved analytical methods for perfluoroalkyl acids (PFAAs) and their precursors – a focus on human dietary exposure
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Per- and polyfluoroalkyl substances are a large group of global environmental contaminants. They can be divided into two sub-groups, 1) perfluoroalkyl acids (PFAAs) and 2) so called precursors, i.e. compounds that can potentially be transformed to form PFAAs. PFAAs are today ubiquitous in wildlife and humans. Food and drinking water are assumed to be the dominant human exposure pathways for PFAAs.

The main aim of this doctoral thesis was to develop highly sensitive and fully validated analytical methods for the determination of a range of PFAAs and selected precursors in dietary samples. The methods were based on liquid chromatography coupled to mass spectrometry. Samples were extracted by solvent extraction followed by a cleanup step employing solid phase extraction. The cleanup step could at the same time be used as a fractionation of ionic PFAAs and neutral precursors.

Paper I and II describe the development of methods for simultaneous analysis of three groups of PFAAs including perfluoroalkyl phosphonic acids (PFPAs) in drinking water and food. Methyl piperidine was used as ion pairing agent, leading to highly sensitive analysis of PFPAs. A first screening of tap water samples and different food items revealed that human dietary exposure to PFPAs in Europe is currently not of concern.

A novel method for simultaneous analysis of perfluoroalkyl carboxylic acids (PFCAs) and polyfluoroalkyl phosphate esters (PAPs) in food and packaging materials is described in paper III. Targeted food samples and their packaging were analyzed. The results showed that PAPs may contribute to human exposure to PFCAs. In paper IV temporal trends (1991-2011) of perfluorooctane sulfonic acid (PFOS) and its precursors in herring were investigated. Rapidly decreasing trends were found for precursors, whereas PFOS did not show a significant change over time. Precursors in fish may have played an important role for human exposure to PFOS in the 1990s but are probably negligible today.

Place, publisher, year, edition, pages
Stockholm: Department of Applied Environmental Science (ITM), Stockholm University, 2013. p. 47
Keywords
Environmental Science, PFASs, PFAAs, PFOA, PFOS, Precursor, FOSA, PAPs, Method development, LC-MS, SPE, Dietary sample, Drinking water, Human exposure
National Category
Environmental Sciences
Research subject
Applied Environmental Science
Identifiers
urn:nbn:se:su:diva-93719 (URN)978-91-7447-753-5 (ISBN)
Public defence
2013-10-25, Nordenskiöldsalen, Geovetenskapens hus, Svante Arrhenius väg 12, Stockholm, 10:00 (English)
Opponent
Supervisors
Projects
PERFOOD project (KBBE-227525)
Funder
EU, FP7, Seventh Framework Programme, KBBE-227525
Note

At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 4: Manuscript.

Available from: 2013-10-03 Created: 2013-09-13 Last updated: 2022-02-24Bibliographically approved

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Gebbink, Wouter A.Ullah, ShahidBerger, Urs

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