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Discussion papers
https://doi.org/10.5194/acp-2018-863
© Author(s) 2018. This work is distributed under
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/acp-2018-863
© Author(s) 2018. This work is distributed under
the Creative Commons Attribution 4.0 License.

Research article 30 Aug 2018

Research article | 30 Aug 2018

Review status
This discussion paper is a preprint. A revision of the manuscript is under review for the journal Atmospheric Chemistry and Physics (ACP).

Measurements of I/SVOCs in biomass-burning smoke using solid-phase extraction disks and two-dimensional gas chromatography

Lindsay E. Hatch1, Albert Rivas-Ubach2, Coty N. Jen3,a, Mary Lipton2, Allen H. Goldstein3,4, and Kelley C. Barsanti1 Lindsay E. Hatch et al.
  • 1Department of Chemical and Environmental Engineering and College of Engineering – Center for Environmental Research and Technology (CE-CERT) , University of California, Riverside, Riverside, CA 92507, USA
  • 2Environmental and Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA, 99352, USA
  • 3Department of Environmental Science, Policy, and Management, University of California, Berkeley, Berkeley, CA, 94720, USA
  • 4Department of Civil and Environmental Engineering, University of California, Berkeley, Berkeley, CA 94720, USA
  • acurrent address: Department of Chemical Engineering, Carnegie Mellon University, Pittsburgh, PA 15289, USA

Abstract. Biomass-burning organic-aerosol (OA) emissions are known to exhibit semi-volatile behavior that impacts OA loading during plume transport. Because such semi-volatile behavior depends in part on OA composition, improved speciation of intermediate and semi-volatile organic compounds (I/SVOCs) emitted during fires is needed to assess the competing effects of primary OA volatilization and secondary OA production. In this study, we sampled 18 laboratory fires in which a range of fuel types were burned. Emitted I/SVOCs were collected onto Teflon filters and solid-phase extraction (SPE) disks to characterize particulate and gaseous I/SVOCs, respectively. Derivatized filter extracts were analyzed using comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (GC×GCTOFMS). Quality control tests were performed using biomass-burning relevant standards and demonstrate the utility of SPE disks for untargeted analysis of air samples. The speciation profiles of I/SVOCs in coniferous fuel-derived smoke samples determined by GC×GCTOFMS were well correlated with each other, but poorly correlated with other fuel types (e.g., herbaceous and chaparral fuels). Benzenediol isomers were also shown to display fuel-dependent emissions. Differences in gas-particle partitioning of the benzenediol isomers were captured using combined Teflon and SPE filter data, with hydroquinone significantly less volatile than catechol. Additionally, the speciated volatility distribution of I/SVOCs in smoke from a rotten-log fire was estimated to evaluate the composition of potentially volatilized primary OA, which was entirely attributed to oxygenated (or other heteroatomic) compounds. Because the chemistry of such compounds has not been extensively studied, more work is needed to assess the relative importance of gas-phase vs. heterogeneous oxidation pathways for biomass-burning-derived I/SVOCs.

Lindsay E. Hatch et al.
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Lindsay E. Hatch et al.
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Short summary
We demonstrate the use of solid-phase extraction disks for the untargeted analysis of gas-phase intermediate volatility and semi-volatile organic compounds emitted from biomass burning. Samples collected from laboratory fires were analyzed by two-dimensional gas-chromatography. We show significant volatility differences among benzenediol isomers and estimate the volatility distribution of compounds emitted from a rotten log fire. The effects of fuel type on emissions are discussed.
We demonstrate the use of solid-phase extraction disks for the untargeted analysis of gas-phase...
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