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155 (6/4) was not detected in the technical mixture
(Fig. 1a–c), Kruger (1988) reported traces of this congener
¨
in THBB without providing structural proof. Regardless, it
is unrealistic that PBB 155 (6/4) will be more enriched than
PBB 153 (6/2), whose chlorinated kin is the most stable
PCB congener in fish. Hence, the PBB residue pattern
determined in cod liver – as dominated by hexaBBs – must
be the consequence of the (partial) reductive debromina-
tion of TOBB and/or TDBB. This is in agreement with
the fact that the 2nd most abundant PBB in THBB –
PBB 180 (7/2) – was only present in traces in the Baltic
cod liver, whereas the chlorinated analogue (PCB 180)
belongs to the most recalcitrant PCB congeners in biota.
Our results also confirm that Br ! H exchange preferen-
tially occurred in meta- and para-positions. Therefore, it
was not surprising that PBB 180 (7/2) was only detected
in traces in the Baltic cod liver.
˚
Herzke, D., Berger, U., Nygard, T., Vetter, W., 2003. Organochlorines,
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In contrast to the results obtained in this study, PBB 153
(6/2) is the PBB congener reported to date in most studies
on PBBs (UNEP, 2006). We suppose that this is rather due
to its availability as a reference standard than the environ-
mental relevance of this hexaBB. It is evident that the
restricted availability of PBB reference standards hinders
the thorough investigation of the environmental fate of
PBBs. Synthesis in the field should focus on tri- and
tetra-ortho PBBs. It is important to note that the major
hexaBB in cod liver – PBB 155 (6/4) – cannot be formed
from any precursor in THBB. In addition, the only parent
compound in TOBB is PBB 209 (10/4). Thus, it is evident
that PBB residues in the Baltic cod liver are the conse-
quence of the previous (unintended) release of TDBB
(PBB 209 (10/4)) into the environment. By contrast, low
concentrations of PBB 155 (6/4) compared to PBB 153
(6/2) reported in biota from the Great Lakes and Japan
(Luross et al., 2002; Watanabe et al., 2004) indicate that
the PBB pollution in these environments was predomi-
nantly caused by the previous application of THBB. It is
thus plausible that selected PBBs and particularly PBB
155 (6/4) can be used as tracer compounds to determine
the original source of pollution, i.e., THBB versus higher
brominated technical PBB mixtures. Dominance of PBB
155 (6/4) points towards the use of TDBB (and to a lesser
degree TOBB), whereas the absence of this key-PBB points
towards THBB. Irrespective of the technical PBB mixtures
used – THBB, TOBB, or TDBB – the PBB residues in mar-
ine fish appear to be dominated by hexaBBs. Thus, these
finding appear to be highly relevant for the understanding
of the environmental fate of PBBs.
Herzke, D., Berger, U., Kallenborn, R., Nygard, T., Vetter, W., 2005.
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¨
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¨
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