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 (GCxGC-ENCI-TOFMS) and to a micro-electron capture detector (GCxGC-mu ECD). GCxGC-ENCI-TOFMS and GCxGC-mu ECD were found to be > 10x more sensitive toward brominated pollutants than conventional GCxGC-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. GCxGC 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.