TitleQuantification of complex polycyclic aromatic hydrocarbon mixtures in standard reference materials using comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry.
Publication TypeJournal Article
Year of Publication2013
AuthorsManzano, C, Hoh, E, Simonich, SLMassey
JournalJ Chromatogr A
Volume1307
Pagination172-9
Date Published2013 Sep 13
ISSN1873-3778
KeywordsEnvironmental Pollutants, Gas Chromatography-Mass Spectrometry, Polycyclic Hydrocarbons, Aromatic, Reference Standards
Abstract

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.

DOI10.1016/j.chroma.2013.07.093
Alternate JournalJ Chromatogr A
PubMed ID23932031
PubMed Central IDPMC4153360
Grant ListHHSN267200700021C / HD / NICHD NIH HHS / United States
HHSN267200700021C / / PHS HHS / United States
P30 ES000210 / ES / NIEHS NIH HHS / United States
P30 ES00210 / ES / NIEHS NIH HHS / United States
P42 ES016465 / ES / NIEHS NIH HHS / United States
P42 ES016465 / ES / NIEHS NIH HHS / United States