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Quantification of Complex Polycyclic Aromatic Hydrocarbon Mixtures in Standard Reference Materials Using GC×GC/ToF-MS

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https://ir.library.oregonstate.edu/concern/articles/sj139257h

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  • 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 isomers 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 without cleanup.
  • Keywords: PAHs, Quantitation of POPs, Comprehensive Two-dimensional Gas Chromatography, ToF-MS, Complex Environmental Samples
  • Keywords: PAHs, Quantitation of POPs, Comprehensive Two-dimensional Gas Chromatography, ToF-MS, Complex Environmental Samples
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  • Manzano, C., Hoh, E., & Simonich, S. L. M. (2013). Quantification of complex polycyclic aromatic hydrocarbon mixtures in standard reference materials using comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry. Journal of Chromatography A, 1307, 172-179. doi:10.1016/j.chroma.2013.07.093
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  • 1307
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  • Funding for this research was provided by the U.S. National Science Foundation (ATM-0841165). This publication was made possible in part by National Institute of Environmental Health Sciences (NIEHS), National Institutes of Health (NIH), grants P30 ES00210 and P42 ES016465 and the National Children’s Study Formative Research Project (HHSN267200700021C, National Institute of Child Health and Human Development).
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