An analytical investigation of 24 oxygenated-PAHs (OPAHs) using liquid and gas chromatography–mass spectrometry

Abstract

We developed two independent approaches for separation and quantitation of 24 oxygenated polycyclic aromatic hydrocarbons (OPAHs) using both liquid chromatography-atmospheric pressure chemical ionization/mass spectrometry (LC-APCI/MS) and gas chromatography-electron impact/mass spectrometry (GC-EI/MS). Building on previous OPAH research, we examined laboratory stability of OPAHs, improved existing method parameters, and compared quantification strategies using standard addition and an internal standard on an environmental sample. Of 24 OPAHs targeted in this research, 19 compounds are shared between methods, with 3 uniquely quantitated by GC-EI/MS and 2 by LC-APCI/MS. Using calibration standards, all GC-EI/MS OPAHs were within 15 % of the true value and had less than 15 % relative standard deviations (RSDs) for interday variability. Similarly, all LC-APCI/MS OPAHs were within 20 % of the true value and had less than 15 % RSDs for interday variability. Instrument limits of detection ranged from 0.18 to 36 ng mL−1 on the GC-EI/MS and 2.6 to 26 ng mL−1 on the LC-APCI/MS. Four standard reference materials were analyzed with each method, and we report some compounds not previously published in these materials, such as perinaphthenone and xanthone. Finally, an environmental passive sampling extract from Portland Harbor Superfund, OR was analyzed by each method using both internal standard and standard addition to compensate for potential matrix effects. Internal standard quantitation resulted in increased precision with similar accuracy to standard addition for most OPAHs using 2-fluoro-fluorenone-13C as an internal standard. Overall, this work improves upon OPAH analytical methods and provides some considerations and strategies for OPAHs as focus continues to expand on this emerging chemical class.FigureOPAH chromatograms from GC-EI/MS and LC-APCI/MS methods for NIST SRM 1650b (diesel particulate matter)Electronic supplementary materialThe online version of this article (doi:10.1007/s00216-013-7319-x) contains supplementary material, which is available to authorized users.

Improvements in pollutant monitoring: Optimizing silicone for co-deployment with polyethylene passive sampling devices

“…Specific method details can be found for PAH (Allan et al, 2012), OPAH (O’Connell et al, 2013), and pesticide (Anderson et al, 2014) analyses published previously. Internal standards for each method were spiked into extract aliquots just prior to instrumental analyses.…”

“…One class of compounds that is well suited for a comparison between silicone and LDPE is oxygenated-PAHs (OPAHs). OPAHs are degradation products of PAHs (Lundstedt et al, 2007), and are emerging contaminants of interest that have log K ow values less than 6 for 22 previously studied OPAHs (O’Connell et al, 2013). Other classes of pollutants, such as pesticides, span a wide range of chemical properties that are also beneficial for polymer comparisons.…”

PAH and OPAH Flux during the Deepwater Horizon Incident

“…10-12 Air sampling is often focused on determining the concentration of particulate bound chemicals; however, exposure to the PAH vapor phase has been shown to account for up to 86% of the cancer-risk from inhalation exposure. 13-15 Vapor phase PAHs are by definition unbound to particulates which means this atmospheric fraction is respirable and bioavailable.…”

In vivo contaminant partitioning to silicone implants: Implications for use in biomonitoring and body burden

“…Interestingly, 9,10-anthraquinone was seen in one explant and is present in petrogenic, pyrogenic, and dye manufacturing sources (NLM 1993), and has even been shown to migrate from pizza boxes into the food item (IARC 2012; NLM 1993)). Anthraquinone is one of the more commonly detected OPAHs in environmental samples (IARC 2012; O’Connell et al 2013), but has not been previously measured in human samples to our knowledge. Another interesting observation was that many of the compounds detected (ex: caffeine, and some phosphate compounds) are known to be metabolized and excreted more rapidly than others.…”