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Synthesis of organobromines as a tool for their characterisation and environmental occurrence assessment
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
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 [en]
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: urn:nbn:se:su:diva-95649ISBN: 978-91-7447-800-6 (print)OAI: oai:DiVA.org:su-95649DiVA: diva2:660986
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
List of papers
1. Synthesis and tentative identification of novel polybrominated diphenyl ether metabolites in human blood
Open this publication in new window or tab >>Synthesis and tentative identification of novel polybrominated diphenyl ether metabolites in human blood
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.

Keyword
Hydroxylated polybrominated diphenylethers (OH-PBDEs), Synthesis, Brominated flame retardants (BFRs), Metabolites
National Category
Chemical Sciences
Research subject
Environmental Chemistry
Identifiers
urn:nbn:se:su:diva-80624 (URN)10.1016/j.chemosphere.2012.03.076 (DOI)000307143800013 ()
Note

AuthorCount:4;

Available from: 2012-09-25 Created: 2012-09-25 Last updated: 2017-12-07Bibliographically approved
2. Synthesis of polybrominated diphenyl ethers via unsymmetrical diaryliodonium triflates
Open this publication in new window or tab >>Synthesis of polybrominated diphenyl ethers via unsymmetrical diaryliodonium triflates
(English)Manuscript (preprint) (Other academic)
Abstract [en]

Polybrominated diphenyl ethers (PBDEs) are ubiquitous environmental pollutants due to theirpersistent character and extensive use as additive flame retardants. In order to assess theirbiological effects, fate, environmental concentrations and other parameters related to riskassessment, authentic PBDE congers are needed for research purposes. In the present work anew general method for the preparation of individual PBDE congeners is presented. Themethodology used is based on recent advances in unsymmetrical diaryliodonium saltsynthesis as well as advances in O-arylation of phenols with these types of salts. Accordingly,three brominated diphenyliodonium triflates were prepared i.e. phenyl(2,4,5-tribromophenyl)iodonium triflate, phenyl(2,4,6-tribromophenyl)iodonium triflate andphenyl(2,3,4,6-tetrabromophenyl)iodonium triflate from 1,2,4-tribromo-5-iodobenzene, 1,3,5-tribromo-2-iodobenzene and 1,2,3,5-tetrabromo-4-iodobenzene, respectively. Yields indiaryliodonium salt syntheses ranged from 69-96%. These salts were further used to O-arylatevarious brominated phenols giving individual tetra- to octa-BDE congeners in yields rangingfrom 64-98%. The O-arylation method used was given after a minor optimisation study, regarding reaction time and temperature, which is reported herein. In addition, this O-arylationmethod was also used with two brominated methoxyphenols in the syntheses of twomethoxylated PBDEs.

National Category
Other Chemistry Topics Organic Chemistry
Research subject
Environmental Chemistry
Identifiers
urn:nbn:se:su:diva-95826 (URN)
Funder
Formas, 2009-1309Formas, 2009-1303
Available from: 2013-11-04 Created: 2013-11-04 Last updated: 2013-11-08
3. Novel Octabrominated Phenolic Diphenyl Ether Identified in Blue Mussels from the Swedish West Coast
Open this publication in new window or tab >>Novel Octabrominated Phenolic Diphenyl Ether Identified in Blue Mussels from the Swedish West Coast
Show others...
2014 (English)In: Environmental Science and Technology, ISSN 0013-936X, E-ISSN 1520-5851, Vol. 48, no 6, 3319-3326 p.Article in journal (Refereed) Published
Abstract [en]

Hydroxylated (OH−) and methoxylated (MeO−) polybrominated diphenyl ethers (PBDEs) are compounds present in the marine environment and OH–PBDEs are of toxicological concern and are therefore of interest to monitor in the environment. A phenolic octaBDE was tentatively identified in the phenolic fraction of previously analyzed mussel samples after methylation of the halogenated phenolic compounds (HPCs). The aim of the present study was to confirm the identity of this compound in blue mussels and investigate whether the analyte is diOH– and/or OH–MeO–octaBDE. Two reference standards, 6,6′-dimethoxy-2,2′,3,3′,4,4′,5,5′-octabromodiphenyl ether (6,6′-diMeO–BDE194) and 6-ethoxy-6′-methoxy-2,2′,3,3′,4,4′,5,5′-octabromodiphenyl ether (6-EtO-6′-MeO–BDE194) were prepared via O-arylation of 2,3,4,5-tetrabromo-6-methoxyphenol and 2,3,4,5-tetrabromo-6-ethoxyphenol, respectively, with a novel unsymmetrical diaryliodonium salt, 2,3,4,5-tetrabromo-6-methoxydiphenyliodonium triflate. The GC retention time and GC/MS spectrum of the synthesized 6,6′-diMeO–BDE194 correspond well with the analyte in the methylated phenolic fraction of a mussel extract from a previous study. Structural analysis performed in this study indicate that the synthesized 6,6′-diMeO–BDE194 and 6-EtO-6′-MeO–BDE194 correspond well with 6-hydroxy-6′-methoxy-2,2′,3,3′,4,4′,5,5′-octabromodiphenyl ether (6-OH–6′-MeO–BDE194) after methylation and ethylation, respectively, of the HPCs in the mussel extracts. The compound 6-OH–6′-MeO–BDE194 was identified and quantified in new mussels, sampled in 2012 from two locations on the Swedish west coast, with geometric mean concentrations of 3700 and 410 ng/g fat, respectively.

National Category
Analytical Chemistry Organic Chemistry Environmental Sciences
Research subject
Environmental Chemistry
Identifiers
urn:nbn:se:su:diva-95828 (URN)10.1021/es404969e (DOI)000333776000029 ()
Funder
Swedish Research Council Formas, 2009-1309Swedish Research Council Formas, 2009-2116Swedish Research Council Formas, 2012-2116
Available from: 2013-11-07 Created: 2013-11-04 Last updated: 2017-12-06Bibliographically approved
4. Occurrence and potential human exposure to brominated flame retardants at a Swedish smelter handling electronic scrap
Open this publication in new window or tab >>Occurrence and potential human exposure to brominated flame retardants at a Swedish smelter handling electronic scrap
(English)Manuscript (preprint) (Other academic)
Abstract [en]

Some well-known brominated flame retardants are common in electronic and electric devices, i.e. polybrominated diphenyl ethers (PBDEs), nowadays particularly the commercial DecaBDE, and tetrabromobisphenol A (TBBPA), but others are used as well. The PBDEs are ubiquitous environmental contaminants while the TBBPA is primarily reported as a contaminant of the abiotic compartments. In this study, personnel at a smelter handling large quantities of shredded printed circuit boards were assessed for potential elevated concentrations of PBDEs, TBBPA and other BFRs. Also dust, sampled at a few sites around the plant, was analysed for BFRs. The dominating BFRs in the dust were decabromodiphenyl ether (BDE-209) and TBBPA, while intermediate levels were indicated for bis(2,4,6-tribromophenoxy)ethane (BTBPE), decabromodiphenyl ethane (DBDPE) and hexabromobenzene (HBB) and only low concentrations of decabromobiphenyl (BB-209) and 2,4,6-tribromophenol (2,4,6-TBP). The workers all showed similar concentrations of the PBDE congeners in serum as recently determined for a Swedish control group. TBBPA was below limit of detection while 2,3,4,6-tetrabromophenol was present in all workers at rather high concentrations. It is yet not known from where this exposure originate, since the compound is not related to BFRs in the dust from the electronic scrap. It is clear that the workers are well protected from the emissions from the printed circuit boards, even though the volumes of electronic scrap handled at the smelter has increased significantly.

National Category
Analytical Chemistry Environmental Sciences
Research subject
Environmental Chemistry
Identifiers
urn:nbn:se:su:diva-95827 (URN)
Available from: 2013-11-04 Created: 2013-11-04 Last updated: 2013-11-08
5. A novel abbreviation standard for organobromine, organochlorine and organophosphorus flame retardants and some characteristics of the chemicals
Open this publication in new window or tab >>A novel abbreviation standard for organobromine, organochlorine and organophosphorus flame retardants and some characteristics of the chemicals
Show others...
2012 (English)In: Environment International, ISSN 0160-4120, E-ISSN 1873-6750, Vol. 49, 57-82 p.Article, review/survey (Refereed) Published
Abstract [en]

Ever since the interest in organic environmental contaminants first emerged 50 years ago, there has been a need to present discussion of such chemicals and their transformation products using simple abbreviations so as to avoid the repetitive use of long chemical names. As the number of chemicals of concern has increased, the number of abbreviations has also increased dramatically, sometimes resulting in the use of different abbreviations for the same chemical. In this article, we propose abbreviations for flame retardants (FRs) substituted with bromine or chlorine atoms or including a functional group containing phosphorus, i.e. BFRs, CFRs and PFRs, respectively. Due to the large number of halogenated and organophosphorus FRs, it has become increasingly important to develop a strategy for abbreviating the chemical names of FRs. In this paper, a two step procedure is proposed for deriving practical abbreviations (PRABs) for the chemicals discussed. In the first step, structural abbreviations (STABs) are developed using specific STAB criteria based on the FR structure. However, since several of the derived STABs are complicated and long, we propose instead the use of PRABs. These are, commonly, an extract of the most essential part of the STAB, while also considering abbreviations previously used in the literature. We indicate how these can be used to develop an abbreviation that can be generally accepted by scientists and other professionals involved in FR related work. Tables with PRABs and STABs for BFRs, CFRs and PERs are presented, including CAS (Chemical Abstract Service) numbers, notes of abbreviations that have been used previously, CA (Chemical Abstract) name, common names and trade names, as well as some fundamental physicochemical constants.

Keyword
Brominated flame retardants, Chlorinated flame retardants, Phosphorus flame retardants, Nomenclature, Abbreviations, Physico-chemical properties
National Category
Chemical Sciences
Research subject
Environmental Chemistry
Identifiers
urn:nbn:se:su:diva-84787 (URN)10.1016/j.envint.2012.08.003 (DOI)000311600500008 ()
Note

AuthorCount:12;

Available from: 2013-01-03 Created: 2013-01-02 Last updated: 2017-12-06Bibliographically approved

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