2. ENVIRONMENTAL ChEMISTRy & TEChNOLOGy 2.1. Lectures

Chem. Listy, 102, s265–s1311 (2008) Environmental Chemistry & Technology
P22 ThE CONTENT OF POLybROMINATED
DIPhENyL EThERS IN FREShwATER FISh
FROM bRNO wATER RESERVOIR
M. HROCH, M. VáVROVá and V. VEČEREK
Faculty of Chemistry, University of Technology Brno, Purkyňova
118, 612 00 Brno, Czech Republic,
hroch@fch.vutbr.cz
Introduction
One group of “new” persistent halogenated contaminants
is represented by brominated flame-retardants (BFRs).
BFRs are chemicals widely used in various products such as
plastics and textiles to prevent a fire hazard. Generally two
types of these compounds are in use. The reactive BFRs
represented mainly by tetrabromobisphenol A (TBBPA) are
incorporated into the polymeric materials by covalent binding,
whereas the additive types, represented by polybrominated
diphenyl ethers (PBDEs), polybrominated biphenyls
(PBBs) and hexabromocyclododecane (HBCD) are embedded
into a matrix of appropriate polymer.
PBDEs are similar to polychlorinated biphenyls (PCBs)
in structure and characteristics such as hydrophobic and
semi-volatile and/or nonvolatile. Theoretically 209 congeners
(5 majorities) of PBDEs exist with specific chemical
and physical properties, which lead to various biological and
toxicological effects. Alike other organohalogen compounds
such as PCBs, DDT and other organochlorine pesticides, PB-
DEs are lipophilic, very stable and resist to acids and basis,
heat and light and biodegradation.
Table I
Physical and chemical characteristics of majority congeners
Congener no. of Br Log Melting Slb. in water
atom K ow point [°C] [mg ml –1 , 25°C]
47 4 6.55 83.5–84.5 0.015
99 5 7.13 90.5–94.5 0.0094
100 5 6.86 102 0.04
154 6 7.39 131–132.5 8.7 × 10 –7
209 10 9.97 302.5 4.17 × 10 –9
The concern over these anthropogenic compounds is
that they can be released into the environment from products
as they are not chemically bounded to the materials, and more
importantly, they are persistent with a high bioaccumulation
potential.
PBDEs are being found as contaminants of indoor and
outdoor environments. The presence of PBDE was proved in
all the components of the environment such as air, sediment
and sewage sludge as well as biological samples including
biota, human blood, adipose tissues and breast milk. Quite
high concentrations were found in the dust in flats and offices.
s378
Experimental
This study presents results of measuring concentration of
ten PBDE congeners (BDE-3, 15, 28, 47, 99, 100, 118, 153,
154 and 183) in different species of fish using gas chromatography
with electron captured detector (GC-ECD). These
samples were collected from Brno water reservoir, which is
situated near the Brno city.
Five head of each kind were detected and the total PBDE
congener concentrations (Σ PBDEs) in the fish were amur <
bream < crucian < carp.
C h e m i c a l s
PBDE standards, all with declared 99% purity, were
purchased from AccuStandard, Inc. (new Haven, USA).
Working standard mixtures in isooctane contained following
congeners: 4-BDE (BDE 3), 4,4’-diBDE (BDE 15),
2,4,4’-triBDE (BDE 28), 2,2’,4,4’-tetraBDE (BDE 47),
2,2’,4,4’,5-pentaBDE (BDE 99), 2,2’,4,4’,6-pentaBDE
(BDE 100), 2,3’,4,4’,5-pentaBDE (BDE 118), 2,2’,4,4’,5,5’hexaBDE
(BDE 153), 2,2’,4,4’,5,6’-hexaBDE (BDE 154),
2,2’,3,4,4’,5’,6-heptaBDE (BDE 183).
M e t h o d
A homogenized fish tissue was desiccated with mixture
of sea sand and anhydrous sodium sulphate. Soxhlet extraction
carried out (6 hours) with hexane/petrolether solvent
mixture (96 : 4, v/v) for isolation of target analytes from the
sample. Concentrated crude extracts were purified by using
multi layer column (300 × 8 mm; florisil, silica, alumina). The
collected fraction was evaporated to dryness and re-dissolved
in 1 ml of isooctane. After addition of a few drops of sulphuric
acid the organic layer was used for GC analysis. Quantification
of target analytes was carried out by high-resolution
gas chromatography, where two capillary columns (DB-17
MS column and HT-8 column) operated in parallel mode
were used. Experiments were carried out on Agilent 6890 GC
system and the analytes were identified by retention times.
Results
This paper reports PBDEs levels in freshwater fish.
These were determined by gas chromatography with ECD.
The identification of PBDEs in the fish samples was based
on comparison of the retention times with those of the available
authenticated standards. All results are summarized in
Fig. 1. Chromatogram of carp-skin sample analysed by GC
with electron captured detector in capillary column Db-17 MS