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
Synthesis and tentative identification of novel polybrominated diphenyl ether metabolites in human blood
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
2012 (English)In: Chemosphere, ISSN 0045-6535, E-ISSN 1879-1298, Vol. 88, no 10, 1227-1234 p.Article in journal (Refereed) Published
Abstract [en]

Hydroxylated polybrominated diphenyl ethers (OH-PDBEs) are exogenous, bioactive compounds that originate, to a large extent, from anthropogenic activities, although they are also naturally produced in the environment. In the present study nine new authentic OH-PBDE reference standards and their corresponding methyl ether derivatives (MeO-PBDEs) were synthesised and characterised by NMR spectroscopy and mass spectrometry. Seven of the authentic reference standards prepared were thereafter tentatively identified in a pooled human blood sample. The tentatively identified OH-PBDEs were 3-hydroxy-2,2',4,4',6-pentabromodiphenyl ether, 3'-hydroxy-2,2',4,4',6-pentabromodiphenyl ether, 3-hydroxy-2,2',4,4',5-pentabromodiphenyl ether, 3-hydroxy-2,2',4,4',5,6'-hexabromodiphenyl ether. 3'-hydroxy-2,2',4,4',5,6'-hexabromodiphenyl ether, 3-hydroxy-2,2',4,4',5,5'-hexabromodiphenyl ether and 4-hydroxy-2,2',3,4',5,5',6-heptabromodiphenyl ether. An additional seven OH-PBDEs were tentatively identified in the pooled human blood sample, of which one OH-PBDE, 4'-hydroxy-2,2',4,5,5'-pentabromodiphenyl ether, has not been identified in human blood before. The identification was performed using gas chromatography-mass spectrometry (GC-MS) recording the bromine ions m/z 79, 81. The tentative identification was supported by the peaks relative retention times (RRTs) compared to authentic references on two GC columns of different polarities for the hexa-, and heptabrominated OH-PBDEs, and three different GC columns for the pentabrominated OH-PBDEs. The OH-PBDE congeners most likely originate from human metabolism of a flame retardant, i.e. polybrominated diphenyl ethers (PBDEs), due to the relatively high concentrations of PBDEs in the same human blood sample and the fact that these PBDEs could form the tentatively identified OH-PBDEs via metabolic direct hydroxylation or via 1,2-shift.

Place, publisher, year, edition, pages
2012. Vol. 88, no 10, 1227-1234 p.
Keyword [en]
Hydroxylated polybrominated diphenylethers (OH-PBDEs), Synthesis, Brominated flame retardants (BFRs), Metabolites
National Category
Chemical Sciences
Research subject
Environmental Chemistry
Identifiers
URN: urn:nbn:se:su:diva-80624DOI: 10.1016/j.chemosphere.2012.03.076ISI: 000307143800013OAI: oai:DiVA.org:su-80624DiVA: diva2:556488
Note

AuthorCount:4;

Available from: 2012-09-25 Created: 2012-09-25 Last updated: 2017-12-07Bibliographically approved
In thesis
1. Synthesis of organobromines as a tool for their characterisation and environmental occurrence assessment
Open this publication in new window or tab >>Synthesis of organobromines as a tool for their characterisation and environmental occurrence assessment
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Polybrominated diphenyl ethers (PBDEs) have been intensively used as flame retardants (FRs) and have become ubiquitous environmental pollutants. PBDEs form hydroxylated PBDEs (OH-PBDEs) as metabolites. Further, some OH-PBDEs and methoxy-PBDEs (MeO-PBDEs) are natural products. These are all compounds of environmental and health concern and it is therefore important to confirm their identity and to assess their environmental levels and toxicities. Hence, it is vital to obtain authentic reference standards of individual PBDEs and OH/MeO-PBDEs. The thesis main aim was to develop synthesis methods of congener specific PBDEs, OH- and MeO-PBDEs. The second aim was to identify and quantify PBDEs, OH- and MeO-PBDEs in environmental samples. The third was to propose an abbreviation system for FRs.

O-Arylation of brominated phenols, using either symmetrical or unsymmetrical brominated diphenyliodonium salts, was selected for synthesis of PBDEs and OH-/MeO-PBDEs. A total of 16 MeO-PBDEs, 11 OH-PBDEs, 1 diMeO-PBDE and 1 EtO-MeO-PBDE were synthesised. Three novel unsymmetrical diaryliodonium triflates were synthesised and used in synthesis. Optimisations were made to construct a reliable general method for congener specific PBDE synthesis, which was used in the synthesis of 8 representative PBDE congeners. The products were generally characterised by electron ionisation mass spectrometry (EIMS) and nuclear magnetic resonance (NMR) spectroscopy.

Identification of PBDEs and OH-PBDEs in various matrixes was based on gas chromatographic and mass spectrometric analyses. Fourteen OH-PBDE congeners were identified in a pooled human blood sample. One previously uncharacterised natural PBDE analogue was identified as 6-OH-6’-MeO-BDE-194, and quantified in Swedish blue mussels. PBDE congeners and other BFRs were identified and quantified in workers and dust from a smelter in Sweden.

A structured and practical abbreviation system was developed for halogen- and phosphorus containing FRs.

Place, publisher, year, edition, pages
Stockholm: Department of Materials and Environmental Chemistry (MMK), Stockholm University, 2013. 85 p.
Keyword
Polybrominated diphenyl ethers, Brominated diphenyliodoniums salts, PBDEs, OH-PBDEs, MeO-PBDEs, Synthesis, Analysis, Abbreviations, Metabolites, Marine natural products, E-waste, Brominated flameretardants
National Category
Other Chemistry Topics
Research subject
Environmental Chemistry
Identifiers
urn:nbn:se:su:diva-95649 (URN)978-91-7447-800-6 (ISBN)
Public defence
2013-12-12, Stora hörsalen, Naturhistoriska riksmuseet, Frescativägen 40, Stockholm, 10:00 (English)
Opponent
Supervisors
Funder
Formas, 2009-1297Formas, 2009-1309Formas, 2009-1303
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Manuscript. Paper 3: Submitted. Paper 4: Manuscript.

Available from: 2013-11-20 Created: 2013-10-31 Last updated: 2013-11-08Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full text

Search in DiVA

By author/editor
Rydén, AndreasMarsh, Göran
By organisation
Department of Materials and Environmental Chemistry (MMK)
In the same journal
Chemosphere
Chemical Sciences

Search outside of DiVA

GoogleGoogle Scholar

doi
urn-nbn

Altmetric score

doi
urn-nbn
Total: 96 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