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

Journal Article · · Atmospheric Chemistry and Physics (Online)

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, 18 laboratory fires were sampled in which a range of fuel types were burned. Emitted I/SVOCs were collected onto Teflon filters and solid-phase extraction (SPE) disks to qualitatively 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 × GC-TOFMS). Quality control tests were performed using biomass-burning relevant standards and demonstrate the utility of SPEdisks for untargeted analysis of air samples. The observed chromatographic profiles of I/SVOCs in coniferous fuel-derived smoke samples were well correlated with each other, but poorly correlated with other fuel types(e.g., herbaceous and chaparral fuels). Emissions of benzenediol isomers were also shown to be fuel dependent. The combined Teflon and SPE filter data captured differences in gas-particle partitioning of the benzene diolisomers, with hydroquinone having a significantly higher particle-phase fraction than catechol due to its lower volatility. 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. The isomer-dependent partitioning and the speciated volatility distributions both suggest the need for better understanding of gas-phase and heterogenous reaction pathways of biomass-burning-derived I/SVOCs in order to represent the atmospheric chemistry of smoke in models.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE Office of Science (SC); USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
Grant/Contract Number:
AC02-05CH11231; AC05-76RL01830
OSTI ID:
1497068
Alternate ID(s):
OSTI ID: 1604659
Report Number(s):
PNNL-SA--137577
Journal Information:
Atmospheric Chemistry and Physics (Online), Journal Name: Atmospheric Chemistry and Physics (Online) Journal Issue: 24 Vol. 18; ISSN 1680-7324
Publisher:
European Geosciences UnionCopyright Statement
Country of Publication:
United States
Language:
English

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