Quantification of complex polycyclic aromatic hydrocarbon mixtures in standard reference materials using comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry

•GC × GC/ToF-MS used for the accurate quantification of complex PAH mixtures in SRMs.•Accurate quantification of 50 or more PAH isomers in one chromatographic run.•Accurate quantification of PAHs in SRMs with minimal or no extract cleanup.•A more comprehensive determination of a complex environmental sample was achieved.•Previously unidentified PAH isomers in both NIST standard reference materials used were reported.

This research is the first to quantify complex PAH mixtures in NIST SRMs using comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC × GC/ToF-MS), with and without extract cleanup, and reports previously unidentified PAH congeners in the NIST SRMs. We tested a novel, high orthogonality GC column combination (LC-50 × NSP-35), as well as with a commonly used column combination (Rtx-5ms × Rxi-17) for the quantification of a complex mixture of 85 different PAHs, including parent (PAHs), alkyl- (MPAHs), nitro- (NPAHs), oxy- (OPAHs), thio- (SPAHs), bromo- (BrPAHs), and chloro-PAHs (ClPAHs) in extracts from two standard reference materials: NIST SRM1650b (diesel particulate matter), with cleanup and NIST SRM1975 (diesel particulate extract), with and without extract cleanup. The LC-50 × NSP-35 column combination resulted in an average absolute percent difference of 33.8%, 62.2% and 30.8% compared to the NIST certified PAH concentrations for NIST SRM1650b, NIST SRM1975 with cleanup and NIST SRM1975 without cleanup, while the Rtx-5ms × Rxi-17 resulted in an absolute percent difference of 38.6%, 67.2% and 79.6% for NIST SRM1650b, NIST SRM1975 with cleanup and NIST SRM1975 without cleanup, respectively. This GC × GC/ToF-MS method increases the number of PAHs detected and quantified in complex environmental extracts using a single chromatographic run. Without clean-up, 7 additional compounds were detected and quantified in NIST SRM1975 using the LC-50 × NSP-35 column combination. These results suggest that the use of the LC-50 × NSP-35 column combination in GC × GC/ToF-MS not only results in better chromatographic resolution and greater orthogonality for the separation of complex PAH mixtures, but can also be used for the accurate quantification of complex PAH mixtures in environmental extracts, such as diesel particulate matter, without silica gel cleanup.