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Analysis of hexafluoropropylene oxide-dimer acid (HFPO-DA) by liquid chromatography-mass spectrometry (LC-MS): Review of current approaches and environmental levels
Örebro University, School of Science and Technology. Waters Corporation, Milford MA, USA. (Man-Technology-Environment Research Centre (MTM))
Atlantic Ecology Division, U.S. Environmental Protection Agency, Narragansett RI, USA.
Wellington Laboratories Inc., Guelph ON, Canada.
Waters Corporation, Milford MA, USA.
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2019 (English)In: TrAC. Trends in analytical chemistry, ISSN 0165-9936, E-ISSN 1879-3142, Vol. 118, p. 828-839Article, review/survey (Refereed) Published
Abstract [en]

Emerging per- and polyfluorinated compounds (PFAS) compounds are of increasing interest for environmental monitoring, one being hexafluoropropylene oxide-dimer acid (HFPO-DA), commonly referred to as GenX. The following review describes existing liquid chromatography-mass spectrometry (LC-MS) methods used to analyse HFPO-DA, including sample preparation and method sensitivity relative to other PFAS. Analytical challenges are also described, in particular the significant formation of in-source fragmentation, dimer and dimer adducts which detract from [M-H](-) signal. Lastly, detected levels of HFPO-DA in environmental and biological samples are compared across the limited number of available field exposure studies, which found several mu g/L concentrations in water samples taken near fluorochemical plant discharges.

Place, publisher, year, edition, pages
Elsevier, 2019. Vol. 118, p. 828-839
Keywords [en]
HFPO-DA, GenX, Negative polarity electrospray ionisation, Liquid chromatography, Mass spectrometry
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:oru:diva-76970DOI: 10.1016/j.trac.2019.05.015ISI: 000486383900064PubMedID: 31501636OAI: oai:DiVA.org:oru-76970DiVA, id: diva2:1356737
Note

Funding Agency:

Intramural EPA  EPA999999

Available from: 2019-10-02 Created: 2019-10-02 Last updated: 2019-10-02Bibliographically approved
In thesis
1. Advances in Mass Spectrometry for the Analysis of Emerging Persistent Organic Pollutants
Open this publication in new window or tab >>Advances in Mass Spectrometry for the Analysis of Emerging Persistent Organic Pollutants
2019 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Mass spectrometry (MS) is a technique widely implemented for the measurement of environmental pollutants. A critical tool for the analysis of persistent organic pollutants (POPs) over several decades, MS as coupled with liquid and gas chromatography (LC and GC) techniques enables the analysis of emerging POPs. The aim of this thesis was to investigate the use of alternative MS-based techniques to assist specific analytical challenges including separation of stereoisomers using supercritical fluid chromatography (SFC), reduced ionization competition with appropriate mobile phase additives, and applied rotationally averaged collision-cross section (CCS) of ions via ion mobility measurements of emerging POPs.

Chromatographic efficiency improvements for the brominated flame retardant, hexabromocyclododecane (HBCDD), were implemented through the development of two supercritical fluid chromatography (SFC) methods. Based on the inherent qualities of supercritical fluids, separation of both predominant diastereomers and respective enantiomers was performed in a shorter time with wider chromatographic resolution using SFC than existing LC methods.

Turning next to MS ionization considerations, the emerging perfluoroalkyl substance hexafluoropropylene oxide-dimer acid (HFPO-DA) was investigated. Following a survey of analytical methodologies for HFPO-DA, the challenge of extreme dimer formation, in-source fragmentation and very low [M-H]- production was described. Method development using alternative mobile phase additives in currently used LC-MS acquisition techniques was deployed.

Finally, ion mobility spectrometry (IMS) was implemented in a non-targeted acquisition study of indoor dust samples. This study used IMS coupled with quadrupole time-of-flight MS to identify a wide range of contaminant classes, including emerging POPs. Identification confidence is a challenge currently facing non-targeted studies, and the use of prediction mechanisms of analyte IMS gas-phase separations was explored.

Through applying diverse alternative techniques, increased method performance was explored for emerging POPs analyses.

Place, publisher, year, edition, pages
Örebro: Örebro University, 2019. p. 83
Series
Örebro Studies in Chemistry, ISSN 1651-4270 ; 24
Keywords
Mass Spectrometry, Liquid Chromatography, Supercritical Fluid Chromatography, Ion Mobility, POPs, Electrospray Ionization
National Category
Other Chemistry Topics
Identifiers
urn:nbn:se:oru:diva-76213 (URN)978-91-7529-303-5 (ISBN)
Public defence
2019-10-25, Örebro universitet, Hörsalen, Musikhögskolan, Fakultetsgatan 1, Örebro, 09:15 (English)
Opponent
Supervisors
Available from: 2019-09-11 Created: 2019-09-11 Last updated: 2019-10-02Bibliographically approved

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Mullin, Lauren GayleYeung, Leo W. Y.Ericson Jogsten, Ingrid

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