Improved separation of the 209 polychlorinated biphenyl congeners using comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry

The separation of the 209 polychlorinated biphenyl (PCB) congeners has been studied using comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC–TOFMS). Four column combinations based on thermally stable phases, DB-1/HT-8, DB-XLB/HT-8, DB-XLB/BPX-50, and HT-8/BPX-50, have been investigated. The HT-8/BPX-50 set produced the best separation. The distribution of the 100 to 150 ms wide peaks was highly structured in the chromatographic space and based on the degree of ortho-substitution within each separated homologue series. A total of 192 congeners were resolved in 146 min (1.3 analyte per min) using this column set. Eight coelutions involved 17 congeners. Among them, seven congeners were present in Aroclors at levels >1.0 wt.% (CBs 33, 47, 48, 95, 97, 163, 187). Except for CBs 47 and 48, none of the major constituents of commercial mixtures were coeluting. CB 138 was well separated from CBs 163 and 164 in the second dimension. For all column sets, CBs 20, 33, and 109 always coeluted with other PCBs. The 12 toxic dioxin-like congeners (CBs 77, 81, 105, 114, 118, 123, 126, 156, 157, 167, 169, 189), and the seven European Union marker PCBs (CBs 28, 52, 101, 118, 138, 153, 180) were separated from any interfering congeners. This was not the case for the other investigated column sets.