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Rapid separation of hexabromocyclododecane diastereomers using a novel method combining convergence chromatography and tandem mass spectrometry
Waters Corporation, Milford, USA.
Waters Corporation, Milford, USA.
Örebro University, School of Science and Technology. (MTM Research Centre)ORCID iD: 0000-0002-6330-789X
Örebro University, School of Science and Technology. (MTM Research Centre)ORCID iD: 0000-0002-8553-8824
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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. Vol. 7, no 7, p. 2950-2958
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
URN: urn:nbn:se:oru:diva-44434DOI: 10.1039/c4ay02923bISI: 000351931000008OAI: oai:DiVA.org:oru-44434DiVA, id: diva2:807675
Available from: 2015-04-24 Created: 2015-04-24 Last updated: 2019-10-09Bibliographically 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, LaurenJogsten, Ingrid EricsonGeng, Daweivan Bavel, Bert

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