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Measurements of I/SVOCs in biomass-burning smoke using solid-phase extraction disks and two-dimensional gas chromatography
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Measurements of I/SVOCs in biomass-burning smoke using solid-phase extraction disks and two-dimensional gas chromatography
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Journal Article
Measurements of I/SVOCs in biomass-burning smoke using solid-phase extraction disks and two-dimensional gas chromatography
2018
Overview
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 SPE
disks 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 benzenediol
isomers, 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.
