Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Improved analytical methods for perfluoroalkyl acids (PFAAs) and their precursors – a focus on human dietary exposure
Stockholm University, Faculty of Science, Department of Applied Environmental Science (ITM).
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. , 47 p.
Keyword [en]
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: urn:nbn:se:su:diva-93719ISBN: 978-91-7447-753-5 (print)OAI: oai:DiVA.org:su-93719DiVA: diva2:648467
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: 2014-01-31Bibliographically approved
List of papers
1. Simultaneous determination of perfluoroalkyl phosphonates, carboxylates, and sulfonates in drinking water
Open this publication in new window or tab >>Simultaneous determination of perfluoroalkyl phosphonates, carboxylates, and sulfonates in drinking water
2011 (English)In: Journal of Chromatography A, ISSN 0021-9673, E-ISSN 1873-3778, Vol. 1218, no 37, 6388-6395 p.Article in journal (Refereed) Published
Abstract [en]

A trace analytical method based on high performance liquid chromatography coupled to quadrupole time-of-flight high resolution mass spectrometry was developed for simultaneous determination of perfluoroalkyl phosphonates (PFPAs, carbon chain lengths C6,8,10), perfluoroalkyl carboxylates (PFCAs. C5-12), and perfluoroalkyl sulfonates (PFSAs. C4,6,8,10) in drinking water (tap water). Analytes were enriched on a mixed mode co-polymeric sorbent (C8 + quaternary amine) using solid phase extraction. Chromatographic separation was achieved on a Zorbax Extend C18 reversed phase column using a mobile phase gradient consisting of water, methanol, and acetonitrile containing 2 mM ammonium acetate and 5 mM 1-methyl piperidine. The mass spectrometer was operated in electrospray negative ion mode. Use of 1-methyl piperidine in the mobile phase resulted in a significant increase in instrument sensitivity for PFPAs through improved chromatographic resolution, background suppression, and increased ionization efficiency. Method detection limits for extraction of 500 mL tap water were in the ranges of 0.095-0.17 ng/L, 0.027-0.17 ng/L, and 0.014-0.052 ng/L for PFPAs. PFCAs, and PFSAs, respectively. Whole method recoveries at a spiking level of 0.5 ng/L to 500 mL HPLC grade water were 40-56%, 56-97%, and 55-77% for PFPAs, PFCAs. and PFSAs, respectively. A matrix effect (signal enhancement) was observed in the detection of PFPAs in tap water extracts, leading to calculated recoveries of 249-297% at a 0.5 ng/L spiking level. This effect resulted in an additional improvement of method sensitivity for PFPAs. To compensate for the matrix effect. PFPAs in tap water were quantified using matrix-matched and extracted calibration standards. The method was successfully applied to the analysis of drinking water collected from six European countries. PFPAs were not detected except for perfluorooctyl phosphonate (PFOPA) at close to the detection limit of 0.095 ng/L in two water samples from Amsterdam, the Netherlands. Highest levels were found for perfluorobutane sulfonate (PFBS, 18.8 ng/L) and perfluorooctanoate (PFOA, 8.6 ng/L) in samples from Amsterdam as well as for perfluorooctane sulfonate (PFOS, 8.8 ng/L) in tap water from Stockholm, Sweden.

Keyword
PFPAs, PFCAs, PFSAs, HPLC/HRMS, Drinking water, 1-Methyl piperidine
National Category
Natural Sciences
Research subject
Applied Environmental Science
Identifiers
urn:nbn:se:su:diva-66521 (URN)10.1016/j.chroma.2011.07.005 (DOI)000295113600020 ()
Note

authorCount :3

Available from: 2011-12-27 Created: 2011-12-20 Last updated: 2017-12-08Bibliographically approved
2. Determination of perfluoroalkyl carboxylic, sulfonic, and phosphonic acids in food
Open this publication in new window or tab >>Determination of perfluoroalkyl carboxylic, sulfonic, and phosphonic acids in food
2012 (English)In: Analytical and Bioanalytical Chemistry, ISSN 1618-2642, E-ISSN 1618-2650, Vol. 404, no 8, 2193-2201 p.Article in journal (Refereed) Published
Abstract [en]

A sensitive and accurate method was developed and validated for simultaneous analysis of perfluoroalkyl carboxylic acids, sulfonic acids, and phosphonic acids (PFPAs) at low picograms per gram concentrations in a variety of food matrices. The method employed extraction with acetonitrile/water and cleanup on a mixed-mode co-polymeric sorbent (C8 + quaternary amine) using solid-phase extraction. High-performance liquid chromatographic separation was achieved on a C18 column using a mobile phase gradient containing 5 mM 1-methyl piperidine for optimal chromatographic resolution of PFPAs. A quadrupole time-of-flight high-resolution mass spectrometer operating in negative ion mode was used as detector. Method detection limits were in the range of 0.002 to 0.02 ng g(-1) for all analytes. Sample preparation (extraction and cleanup) recoveries at a spiking level of 0.1 ng g(-1) to a baby food composite were in the range of 59 to 98 %. A strong matrix effect was observed in the analysis of PFPAs in food extracts, which was tentatively assigned to sorption of PFPAs to the injection vial in the solvent-based calibration standard. The method was successfully applied to a range of different food matrices including duplicate diet samples, vegetables, meat, and fish samples.

Keyword
PFCAs, PFSAs, PFPAs, Food samples, HPLC, HRMS
National Category
Biochemistry and Molecular Biology
Research subject
Applied Environmental Science
Identifiers
urn:nbn:se:su:diva-83037 (URN)10.1007/s00216-012-6374-z (DOI)000310083900012 ()
Note

AuthorCount:4;

Available from: 2012-12-05 Created: 2012-12-03 Last updated: 2017-12-07Bibliographically approved
3. Polyfluoroalkyl phosphate esters and perfluoroalkyl carboxylic acids in target food samples and packaging - method development and screening
Open this publication in new window or tab >>Polyfluoroalkyl phosphate esters and perfluoroalkyl carboxylic acids in target food samples and packaging - method development and screening
2013 (English)In: Environmental Science and Pollution Research, ISSN 0944-1344, Vol. 20, no 11, 7949-7958 p.Article 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.

Keyword
PAPs, FOOD, Precursor, PFCAs, method development, LC-MSMS
National Category
Environmental Sciences
Research subject
Applied Environmental Science
Identifiers
urn:nbn:se:su:diva-93741 (URN)10.1007/s11356-013-1596-y (DOI)000325811600040 ()
Available from: 2013-09-15 Created: 2013-09-15 Last updated: 2013-11-25Bibliographically approved
4. Temporal trends of perfluoroalkane sulfonic acids and their sulfonamide-based precursors in herring from the Swedish west coast 1991–2011 including isomer-specific considerations
Open this publication in new window or tab >>Temporal trends of perfluoroalkane sulfonic acids and their sulfonamide-based precursors in herring from the Swedish west coast 1991–2011 including isomer-specific considerations
(English)Manuscript (preprint) (Other academic)
Abstract [en]

A method was developed for simultaneous analysis of perfluoroalkane sulfonic acids (PFSAs) and their sulfonamide-based precursors (perfluoroalkane sulfonamidoacetic acids (FASAAs), sulfonamides (FASAs), and sulfonamidoethanols (FASEs)) in fish muscle. Extraction was performed with acetonitrile followed by a clean-up and fractionation step and instrumental analysis by UPLC/MS/MS and GC/MS. Time trends of PFSAs and their precursors in herring muscle samples originating from the Kattegat at the west coast of Sweden were investigated covering the years 1991-2011. PFSAs, FOSA and alkyl-FOSAAs were detected at pg/g levels, all with decreasing or unchanged trends between 1991 and 2011. The highest concentrations were found for PFOS and FOSA around the turn of the century. Shorter disappearance half-lives were observed for precursors compared to PFSAs. Assuming that these trend differences are representative for fish consumed by the general Swedish population, this observation suggests that the relative contribution of precursors to total human exposure to PFOS via fish intake has decreased in Sweden over the study period. PFOS precursors in fish may have constituted a significant indirect exposure pathway for PFOS in the 1990s. Isomer-specific analysis of PFOS and FOSA revealed diverging patterns and temporal trends from what is commonly found in human serum. In combination with literature data on isomer patterns in other edible fish species and on isomer-specific human toxicokinetics, our results suggest that fish consumption alone cannot account for the PFOS isomer patterns and trends observed in humans.

Keyword
Temporal trends, herring muscle, PFOS, perfluorooctane sulfonamides, precursor, human exposure
National Category
Environmental Sciences
Research subject
Applied Environmental Science
Identifiers
urn:nbn:se:su:diva-93742 (URN)
Available from: 2013-09-15 Created: 2013-09-15 Last updated: 2013-09-16Bibliographically approved

Open Access in DiVA

Shahid Ullah Thesis 2013(1284 kB)2324 downloads
File information
File name ATTACHMENT02.pdfFile size 1284 kBChecksum SHA-512
abdfe29862dbbf1f1f5e4cd2f26f8c3e9d6b656f80242d3feb3d652ee03c39cc39fec875bfd0c78c144e2106bd352497183cb756e268a442865853ce17fe5919
Type fulltextMimetype application/pdf

Search in DiVA

By author/editor
Ullah, Shahid
By organisation
Department of Applied Environmental Science (ITM)
Environmental Sciences

Search outside of DiVA

GoogleGoogle Scholar
Total: 0 downloads
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

isbn
urn-nbn

Altmetric score

isbn
urn-nbn
Total: 233 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf