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Analysis of Brominated Flame Retardants by
Liquid Chromatography Mass Spectrometry
By Dr. Chris Marvin, Environment Canada
Innovators in Chromatography
A continuing series of guest editorials contributed by collaborators and internationally recognized leaders in chromatography.
Dr. Chris Marvin is a Research Scientist for Environment Canada, Burlington, Ontario. His
research interests include new and emerging environmental contaminants, occurrence and
fate of contaminants in the Great Lakes, and LC-MS methods development.
Awide variety of brominated flame
retardants (BFRs) are currently
used in industry and commerce.
Use of these compounds has increased
exponentially in the past 50 years as a
result of strict regulations regarding the
flame retardancy of consumer products.
Roughly 40% of all flame retardants on
the market are brominated. Some of
these compounds have the potential
to be persistent, toxic, bioaccumula-
tive, and are amenable to long range
transport. In addition, the occurrence,
distribution, and fate of many of these
compounds in the environment remain
largely unknown.
Polybrominated diphenyl ethers (PBDEs)
remain the most widely studied of
the BFRs, despite the penta- and octa-
formulations being banned in Europe
and voluntary cessation of production
in North America. With the exception of
the fully-substituted decabromodiphe-
nyl ether (BDE-209), the PBDEs are easily
determined by gas chromatography-
mass spectrometry (GC-MS) and are
now routinely measured in a wide range
of environmental matrices. Due to its
unique chemical and physical proper-
ties, including high molecular weight,
poor solubility, and sensitivity to heat
and light, accurate determination of
BDE-209 remains a significant challenge.
A host of other BFRs are not readily ame-
nable to analysis by GC-MS and pose
an analytical challenge as a result of
their physical properties. Although their
chemical structures appear quite simple,
BFRs such as hexabromocyclododecane
(HBCD), 1,2,5,6-tetrabromocycloctane
(TBCO) and tetrabromoethylcyclohex-
ane (TBECH) thermally isomerize and
partition poorly on GC stationary phas-
es. HBCD is one of the most widely used
BFRs with production globally in excess
of 20,000 tons; HBCD is the primary
flame retardant used in the extruded
and expanded polystyrene foams used
as thermal insulation in buildings, as
well as in upholstery fabrics. Some
laboratories continue to report HBCD
concentrations as the sum of the three
predominant isomers based on analysis
by GC, i.e., the sum of α-, β- and γ-HBCD.
These nonisomer specific analyses pre-
clude thorough investigation of environ-
mental pathways, and potential shifting
of isomer profiles during manufacture or
cycling in the environment. Differences
in pathways of HBCD in the environment
are evidenced by the predominance of
γ-HBCD in the technical mixture and in
sediment, while α-HBCD is dominant in
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