Fingerprinting polychlorinated biphenyls in environmental samples using comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry

• 188 out of 209 PCBs separated for quantification in one analytical run.
• 200 out of 209 PCBs identified in one analytical run.
• All PCBs separated in Aroclors A1254 and A1260.
• 137 individual congeners identified in a whiting liver sample.
• The results highlight the potential of this method for PCB fingerprinting.

A GC × GC-TOFMS installed with a Rtx-PCB (60 m × 0.18 mm × 0.18 μm) in the first dimension and Rxi-17 (1.5 m × 0.1 mm × 0.1 μm) column in the second dimension was used to separate 188 out of 209 congeners. A further 12 congeners were identified through additional data processing resulting in the identification of a total of 200 congeners. However, caution is advised if these 12 congeners were to be used in quantitative assessments. The remaining 9 co-eluting congeners were three doublets (CB65 + CB62, CB160 + CB163 and CB201 + CB204) and one triplet (CB20 + CB21 + CB33). This method was tested on five Aroclors and resulted in the separation of all congeners present in the heavier Aroclor mixtures A1254 and A1260. The suitability of this method for applications in biological matrices was demonstrated on extracted whiting and guillemot liver samples which resulted in the identification of 137 individual PCBs in the whiting liver sample and 120 in the guillemot sample. Fingerprinting was able to show clear differences in the PCB signature of the two animals. This highlights the potential of this method for PCB fingerprinting in environmental forensics studies and other assessments that require congener specific analysis.