oru.sePublications
Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • 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
Advances in Mass Spectrometry for the Analysis of Emerging Persistent Organic Pollutants
Örebro University, School of Science and Technology.
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 [en]
Mass Spectrometry, Liquid Chromatography, Supercritical Fluid Chromatography, Ion Mobility, POPs, Electrospray Ionization
National Category
Other Chemistry Topics
Identifiers
URN: urn:nbn:se:oru:diva-76213ISBN: 978-91-7529-303-5 (print)OAI: oai:DiVA.org:oru-76213DiVA, id: diva2:1350194
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
List of papers
1. Rapid separation of hexabromocyclododecane diastereomers using a novel method combining convergence chromatography and tandem mass spectrometry
Open this publication in new window or tab >>Rapid separation of hexabromocyclododecane diastereomers using a novel method combining convergence chromatography and tandem mass spectrometry
Show others...
2015 (English)In: Analytical Methods, ISSN 1759-9660, E-ISSN 1759-9679, Vol. 7, no 7, p. 2950-2958Article in journal (Refereed) Published
Abstract [en]

Analysis of the brominated flame retardant hexabromocyclododecane (HBCDD) is characterized by the separation of its three predominant diastereomers. This analysis is typically performed using reversed phase liquid chromatography (RPLC) coupled with mass spectrometric (MS) detection with analysis times in the order of 10 minutes or greater. Here we describe a rapid method using supercritical CO2 and methanol to baseline separate the three most abundant HBCDD diastereomers within a three minute run time using a High Strength Silica (HSS) C18 1.8 mu m particle size column. A unique elution order of the alpha-, beta- and gamma-HBCDD diastereomers using supercritical CO2 was observed, and can be used as an orthogonal separation for further confidence in diastereomer identification when used in conjuction with RPLC. A tandem quadrupole mass spectrometer with negative mode electrospray ionization was used for detection, operating in multiple reaction monitoring (MRM) mode. Ionization was enhanced by the addition of a make-up flow, which was introduced to the post-column effluent. Method limit of detection (LOD) and limit of quantification (LOQ) for alpha-, beta- and gamma-HBCDD were based on peak-to-peak signal to noise ratios of greater than 3 or 10, respectively. The LOD for all HBCDD diastereomers as solvent standards was 100 fg on-column, and LOQs 500 fg on-column for alpha- and gamma-HBCDD and 250 fg on-column for beta-HBCDD. In order to test the efficiency of this method, small subsets of complex human serum and whale blubber extracts were analyzed using this method, resulting in positive detections in samples of alpha-HBCDD.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2015
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:oru:diva-44434 (URN)10.1039/c4ay02923b (DOI)000351931000008 ()
Available from: 2015-04-24 Created: 2015-04-24 Last updated: 2019-10-09Bibliographically approved
2. Enantioselective Analytical- and Preparative-Scale Separation of Hexabromocyclododecane Stereoisomers Using Packed Column Supercritical Fluid Chromatography
Open this publication in new window or tab >>Enantioselective Analytical- and Preparative-Scale Separation of Hexabromocyclododecane Stereoisomers Using Packed Column Supercritical Fluid Chromatography
Show others...
2016 (English)In: Molecules, ISSN 1420-3049, E-ISSN 1420-3049, Vol. 21, no 11, article id 1509Article in journal (Refereed) Published
Abstract [en]

Hexabromocyclododecane (HBCDD) is an additive brominated flame retardant which has been listed in Annex A of the Stockholm Convention for elimination of production and use. It has been reported to persist in the environment and has the potential for enantiomer-specific degradation, accumulation, or both, making enantioselective analyses increasingly important. The six main stereoisomers of technical HBCDD (i.e., the (+) and (-) enantiomers of α-, β-, and γ-HBCDD) were separated and isolated for the first time using enantioselective packed column supercritical fluid chromatography (pSFC) separation methods on a preparative scale. Characterization was completed using published chiral liquid chromatography (LC) methods and elution profiles, as well as X-ray crystallography, and the isolated fractions were definitively identified. Additionally, the resolution of the enantiomers, along with two minor components of the technical product (δ- and ε-HBCDD), was investigated on an analytical scale using both LC and pSFC separation techniques, and changes in elution order were highlighted. Baseline separation of all HBCDD enantiomers was achieved by pSFC on an analytical scale using a cellulose-based column. The described method emphasizes the potential associated with pSFC as a green method of isolating and analyzing environmental contaminants of concern.

Place, publisher, year, edition, pages
Basel, Switzerland: MDPI AG, 2016
Keywords
hexabromocyclododecane, enantiomeric separation, supercritical fluid chromatography
National Category
Analytical Chemistry
Identifiers
urn:nbn:se:oru:diva-53487 (URN)10.3390/molecules21111509 (DOI)000389918200091 ()27834934 (PubMedID)2-s2.0-84997428723 (Scopus ID)
Available from: 2016-11-15 Created: 2016-11-14 Last updated: 2019-10-02Bibliographically approved
3. Analysis of hexafluoropropylene oxide-dimer acid (HFPO-DA) by liquid chromatography-mass spectrometry (LC-MS): Review of current approaches and environmental levels
Open this publication in new window or tab >>Analysis of hexafluoropropylene oxide-dimer acid (HFPO-DA) by liquid chromatography-mass spectrometry (LC-MS): Review of current approaches and environmental levels
Show others...
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
Keywords
HFPO-DA, GenX, Negative polarity electrospray ionisation, Liquid chromatography, Mass spectrometry
National Category
Chemical Sciences
Identifiers
urn:nbn:se:oru:diva-76970 (URN)10.1016/j.trac.2019.05.015 (DOI)000486383900064 ()31501636 (PubMedID)
Note

Funding Agency:

Intramural EPA  EPA999999

Available from: 2019-10-02 Created: 2019-10-02 Last updated: 2019-10-02Bibliographically approved
4. Ionization Enhancement of Hexafluoropropylene oxide dimer acid (HFPO-DA) Through Mobile Phase Additive Selection
Open this publication in new window or tab >>Ionization Enhancement of Hexafluoropropylene oxide dimer acid (HFPO-DA) Through Mobile Phase Additive Selection
Show others...
(English)Manuscript (preprint) (Other academic)
National Category
Other Chemistry Topics
Identifiers
urn:nbn:se:oru:diva-76979 (URN)
Available from: 2019-10-02 Created: 2019-10-02 Last updated: 2019-10-02Bibliographically approved
5. Liquid Chromatography-Ion Mobility-High Resolution Mass Spectrometry for Analysis of Pollutants in Indoor Dust: Identification and Predictive Capabilities
Open this publication in new window or tab >>Liquid Chromatography-Ion Mobility-High Resolution Mass Spectrometry for Analysis of Pollutants in Indoor Dust: Identification and Predictive Capabilities
Show others...
(English)Manuscript (preprint) (Other academic)
National Category
Other Chemistry Topics
Identifiers
urn:nbn:se:oru:diva-76980 (URN)
Available from: 2019-10-02 Created: 2019-10-02 Last updated: 2019-10-02Bibliographically approved

Open Access in DiVA

Cover(139 kB)5 downloads
File information
File name COVER01.pdfFile size 139 kBChecksum SHA-512
e4ad9803d2579a00a7705b0eac7ce4c37165c74af8c059ccfd19188c588c3f12220db6e0c39660dd3e202e9a9052c5bbf55bc4ad17f6fe808bce603a16987ea2
Type coverMimetype application/pdf
Advances in Mass Spectrometry for the Analysis of Emerging Persistent Organic Pollutants(1261 kB)37 downloads
File information
File name FULLTEXT01.pdfFile size 1261 kBChecksum SHA-512
736fd57d8827518bc730bde498f6c6fcb3719633ab4af111fe6533e3f95fce7148a17ea3b7018624ec42eaa89c15386c54288112b340209c2ee28aff9ced6d3d
Type fulltextMimetype application/pdf
Spikblad(101 kB)2 downloads
File information
File name SPIKBLAD01.pdfFile size 101 kBChecksum SHA-512
558abbc1974bfd6a16721968759e608036768344f3afa2f0476c7ca0cee433b028fefa873a22de8bc6c60fbb1b7904ce6b4062ded23c94658ed327ff22053c96
Type spikbladMimetype application/pdf

Authority records BETA

Mullin, Lauren Gayle

Search in DiVA

By author/editor
Mullin, Lauren Gayle
By organisation
School of Science and Technology
Other Chemistry Topics

Search outside of DiVA

GoogleGoogle Scholar
Total: 37 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: 250 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • 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