We quantified the
concentrations of two little-studied brominated
pollutants, 1,3,5-tribromobenzene (TBB) and 4-bromobiphenyl (4BBP),
in the deep water column and sediments of Lake Geneva. We found aqueous
concentrations of 625 ± 68 pg L
–1
for TBB and
668 ± 86 pg L
–1
for 4BBP over a depth range
of 70–191.5 m (near-bottom depth), based on duplicate measurements
taken at five depths during three separate 1 month sampling periods
at our sampling site near Vidy Bay. These levels of TBB and 4BBP were
1 or 2 orders of magnitude higher than the quantified aqueous concentrations
of the components of the pentabrominated biphenyl ether technical
mixture, which is a flame retardant product that had a high production
volume in Europe before 2001. We observed statistically significant
vertical concentration trends for both TBB and 2,2′,4,4′,6-pentabromobiphenyl
ether in the deep water column, which indicates that transport and/or
degradation processes affect these compounds. These measurements were
enabled by application of a comprehensive two-dimensional gas chromatograph
coupled to an electron capture negative chemical ionization time-of-flight
mass spectrometer (GC×GC-ENCI-TOFMS) and to a micro-electron
capture detector (GC×GC-μECD). GC×GC-ENCI-TOFMS and
GC×GC-μECD were found to be >10× more sensitive
toward
brominated pollutants than conventional GC×GC-EI-TOFMS (with
an electron impact (EI) ionization source), the latter of which had
insufficient sensitivity to detect these emerging brominated pollutants
in the analyzed samples. GC×GC also enabled the estimation of
several environmentally relevant partitioning properties of TBB and
4BBP, further confirming previous evidence that these pollutants are
bioaccumulative and have long-range transport potential.