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Identification and Quantification of 4-Nitrocatechol Formed from OH and NO Radical-Initiated Reactions of Catechol in Air in the Presence of NO: Implications for Secondary Organic Aerosol Formation from Biomass Burning 3
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Zachary Finewax, Joost A. de Gouw, and Paul J. Ziemann Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.7b05864 • Publication Date (Web): 22 Jan 2018 Downloaded from http://pubs.acs.org on January 24, 2018
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Identification and Quantification of 4-Nitrocatechol Formed from OH and NO3
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Radical-Initiated Reactions of Catechol in Air in the Presence of NOx:
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Implications for Secondary Organic Aerosol Formation from Biomass Burning
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Zachary Finewax†, §, Joost A. de Gouw§, ζ, Paul J. Ziemann†, § *
9 10 11 12 13 14 15 16 17 18 19
Submitted to Environmental Science and Technology
20 21 22
†
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United States
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§
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Boulder, Colorado 80309, United States
26
ζ
27
80305, United States
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*
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Telephone: 303-492-9654
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Fax: 303-492-1149
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Email:
[email protected]
Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309,
Cooperative Institute for Research in Environmental Sciences (CIRES), University of Colorado,
Chemical Sciences Division, NOAA Earth System Research Laboratory, Boulder, Colorado
Author to whom correspondence should be addressed.
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ABSTRACT Catechol (1,2-benzenediol) is emitted from biomass burning and produced from reaction
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of phenol with OH radicals. It has been suggested as an important secondary organic aerosol
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(SOA) precursor, but the mechanisms of gas-phase oxidation and SOA formation have not been
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investigated in detail. In this study, catechol was reacted with OH and NO3 radicals in the
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presence of NOx in an environmental chamber to simulate daytime and nighttime chemistry.
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These reactions produced SOA with exceptionally high mass yields of 1.34 ± 0.20 and 1.50 ±
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0.20, respectively, reflecting the low volatility and high density of reaction products. The
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dominant SOA product, 4-nitrocatechol, for which an authentic standard is available, was
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identified through thermal desorption particle beam mass spectrometry and Fourier transform
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infrared spectroscopy, and was quantified in filter samples by liquid chromatography using UV
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detection. Molar yields of 4-nitrocatechol were 0.30 ± 0.03 and 0.91 ± 0.06 for reactions with
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OH and NO3 radicals, and thermal desorption measurements of volatility indicate that it is semi-
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volatile at typical atmospheric aerosol loadings, consistent with field studies that have observed
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it in aerosol particles. Formation of 4-nitrocatechol is initiated by abstraction of a phenolic H-
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atom by an OH or NO3 radical to form a β-hydroxyphenoxy/o-semiquinone radical, which then
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reacts with NO2 to form the final product.
49 50 51
INTRODUCTION Biomass burning is a significant source of atmospheric gas- and particle-phase emissions
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worldwide.1 Biomass burning can be anthropogenic (heating, cooking, prescribed forest fire
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burns) or natural (lightning propagated wildfires).2 The aerosol emitted from biomass burning
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can impact regional air quality and regional and global climate through long-range transport,
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depending on the strength of convection in the plume.3 In addition to the primary organic aerosol
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(POA) that is directly emitted from wildfires, secondary organic aerosol (SOA) can be formed
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when emissions of volatile organic compounds (VOCs) are oxidized to condensable products.
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Field studies have shown mixed results for O3 and aerosol formation in wildfire plumes, with
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some studies indicating formation and others showing net losses.4-6 Furthermore, POA emissions
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and SOA production from biomass burning are highly variable and depend on the type of fuel
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burned.4 These findings show that the mechanisms of SOA formation from wildfire emissions
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are complex, and may be difficult to model.
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To date, a number of studies have been conducted to identify and quantify the complex
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mixture of VOCs emitted from combustion of different types of biomass,7-9 but the fate of these
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compounds with respect to reactions in the atmosphere and SOA formation is much less certain.
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In one approach, Gilman et al.9 used their measurements of VOCs emitted from controlled
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biomass burns with compound-specific SOA formation potentials (derived by Derwent et al.10
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using the Master Chemical Mechanism11) to estimate total SOA formation potentials for
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individual compounds and various compound classes. In light of unexplained enhancements and
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suppressions of O3, and organic aerosol observed in numerous wildfire plumes, however, it is
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apparent that the chemistry occurring within these plumes needs to be systematically investigated
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to better constrain the processes leading to these observations.
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1,2-Benzenediol, commonly known as catechol, is emitted directly from biomass
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burning12 as well as produced in the atmosphere through the gas-phase reaction of benzene and
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phenol with OH radicals.13,14 The emission of catechol from wildfires is due to pyrolysis of
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lignin, a polymer in wood containing phenolic moieties.15 Catechol displays appreciable gas-
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phase reactivity. Using average concentrations (molecules cm-3) of 2 × 106 (0.1 ppt), 7 × 1011 (30
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ppb), and 5 × 108 (20 ppt) for OH (12-h daytime), O3 (24-h), and NO3 (12-h nighttime),
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respectively,16 and corresponding reaction rate constants of 1.0 × 10-10, 9.6 × 10-18, and 9.8 × 10-
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11
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studies have shown that catechol produces large quantities of SOA when reacted with O3 and OH
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radicals,20,21 and it has been predicted to be one of the main precursors to SOA formation from
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wildfire emissions.9 A study of gas-phase reaction products has shown that under moderate NOx
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conditions, reaction with OH radicals forms significant amounts of 4-nitrocatechol (4NC),21 and
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the Master Chemical Mechanism (MCM v3.1) assumes that 4NC is the sole reaction product.11
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To our knowledge, however, the yield of 4NC has not been measured for reactions of catechol
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with OH or NO3 radicals in the presence of NOx.
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cm3 molecule-1 s-1,17-19 estimated atmospheric lifetimes are 1.4 h, 1.7 d, and 20 s. Chamber
In this study, catechol was reacted with OH and NO3 radicals in the presence of NOx to
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determine yields of SOA and reaction products as well as reaction mechanisms under simulated
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daytime and nighttime conditions. The vapor pressure of 4NC, the major SOA product in these
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reactions, was measured for use in predicting its fate and possible environmental impacts.
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Because of the large catechol emission factors for combustion of biomass,12 and its relatively
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high predicted SOA formation potential,9 catechol may be responsible for an appreciable portion
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of the SOA produced from wildfires.
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MATERIALS AND METHODS
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Chemicals. The chemicals used, with purities or solvent grades and supplier were
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methanol, ethyl acetate, and acetonitrile (HPLC grade, EMD Millipore); water (HPLC grade,
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Fisher Chemical); catechol (+99%, Sigma Aldrich); 4-nitrocatechol (97%, Sigma Aldrich);
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glacial acetic acid (99.7%, Macron); dioctyl sebacate (>97%, Fluka); and nitric oxide (99%,
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Matheson Tri-gas). Methyl nitrite and N2O5 were synthesized according to the procedures of
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Taylor et al.22 and Atkinson et al,23 respectively. Methyl nitrite was stored in a lecture bottle on a
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vacuum manifold until used, and N2O5 was stored in a –80°C freezer and placed on a vacuum
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manifold when used.
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Environmental Chamber Experiments. Catechol reactions were conducted at 25 °C
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and 630 Torr in an 8.0 m3 FEP Teflon environmental chamber filled with dry, clean air (RH <
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1%, VOCs and NOx 96% of 4NC was in particles. In addition, we note
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that although there are significant uncertainties in the quantities that contribute to this
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calculation, if the true value was significantly less than 96%, then one would expect that the
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measured 4NC yields would increase with increased aerosol mass concentration because of
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enhanced partitioning of 4NC from the gas phase to the particles. But since the 4NC yields for
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the OH radical-initiated reactions are essentially independent of SOA mass concentration from
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300 to 2500 ug m-3 (the four experiments shown in Table 1), the 4NC appears to be almost
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entirely in the particle phase in all experiments. This result thus supports our assumption that the
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molar yield of 4NC determined from particle analysis is essentially equal to the total molar yield.
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The molar yields of 4NC measured for reactions of catechol with OH and NO3 radicals were
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0.30 ± 0.03 and 0.91 ± 0.06, respectively (Table 1). The much higher 4NC yield for the NO3
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radical reaction is consistent with the much greater similarity in SOA mass spectra (Figure 1),
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TPTD profiles (Figure S6), and ATR-FTIR spectra (Figure 2). Because of the nonlinear
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dependence of ATR-FTIR spectral intensity on species concentration, due to film thickness
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effects, no attempt was made to quantify the yield of 4NC in SOA by this method or to compare
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the ATR-FTIR spectra quantitatively between 4NC and the filter extract. It is also worth noting
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that although both reactions produced colored aerosol (Figure S7), SOA formed from the OH
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radical reaction was orange/brown whereas SOA formed from the NO3 radical reaction was light
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yellow: the color of 4NC.
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One of the additional components of SOA formed from the OH radical reaction appears
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to be 5-nitro-1,2,3-benzenetriol. The presence of this compound is indicated by the molecular ion
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peak at m/z 171 in the TDPBMS mass spectrum (Figure 1A), which is absent from the mass
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spectrum of SOA formed from the NO3 radical reaction (Figure 1B). Furthermore, when one of
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the SOA components fractionated by HPLC (Figure S8)was analyzed by CI-ITMS, the mass
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spectrum (Figure S9) contained peaks at m/z 172 [M + H]+, 155 [M + H – OH]+, 141 [M + H –
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NO]+, 126 [M + H – NO2]+, and 108 [M + H – NO2 – H2O]+, which are all consistent with this
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product. For nitroaromatic compounds, loss of NO and NO2 from the protonated molecular ion is
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enhanced if electron donating groups are located meta to the –NO2 group, whereas loss of H2O is
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enhanced when an electron withdrawing –OH group is located ortho to the –NO2 group.45
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Because of the very low signal at m/z 154, which corresponds to the [M + H – H2O]+ ion that
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would be formed by the latter pathway, the only arrangement of one –NO2 and three –OH groups
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on the ring that remains possible is 5-nitro-1,2,3-benzenetriol. The measured molar yield of 5-
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nitro-1,2,3-benzenetriol was 0.04 ± 0.01.
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The sum of the mass yields (mass of product formed/mass of catechol reacted) of 4NC
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(0.42) and 5-nitro-1,2,3-benzenetriol (0.06) formed in the OH radical reaction was 0.48, which is
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much lower than the mass yield of SOA (see discussion below) of 1.34, and indicates that only
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~35% of the SOA products are accounted for in the molecular analysis. In an attempt to further
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characterize the unidentified components of SOA formed in the OH radical reaction, the SOA
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was reacted with 2,4-dinitrophenylhydrazine (DNPH) to convert compounds containing carbonyl
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groups to hydrazones that can be detected by their UV-Vis absorbance.33,46 The ATR-FTIR
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spectrum of the underivatized SOA (Figure 2) indicated that compounds with carbonyl groups
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were present, due to absorbance at 1600–1700 cm-1, and would be indicative of ring-opened
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products. The C-H stretching at 2900 – 3000 cm-1 may be additional evidence of ring-opened
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products, but is largely from DOS seed particles. Peaks in HPLC chromatograms (Figure S9)
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obtained at 360 nm and 430 nm indicated the presence of monofunctional and difunctional
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carbonyls,46 but CI-ITMS analysis was unsuccessful at identifying these compounds due to the
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complex mass spectra. Based on these results, it is likely that the SOA contained hemiacetals and
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acetals formed from reactions involving ring-opened products. This is supported by the
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observation of broad peaks from ~60–150oC in the TPTD profiles of total ion signal
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(proportional to aerosol mass) beyond the 4NC peak at 39oC (Figure S6A).
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SOA Yields. The yields of SOA formed from reactions of catechol with OH and NO3
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radicals were 1.34 ± 0.2 and 1.50 ± 0.2, with uncertainties reported as the standard deviation of 4
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and 2 replicate experiments, respectively, and are given in Table 1. These values are
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exceptionally high, considering that those measured for the photooxidation of simple aromatics
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ranged from about 0 to 0.14,47 whereas those measured for reactions of biogenic compounds with
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OH and NO3 radicals and O3 ranged from 0 to 0.9.48 Yields can be larger than 1.0 because they
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are based on the mass of SOA formed relative to the mass of catechol reacted, and the SOA
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products contain mass from O and N that was not associated with catechol. Note also that the
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yield of 1.50 for the reaction with NO3 radicals is equivalent to a molar yield of 4NC of 1.06
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(assuming the SOA is pure 4NC), consistent within measurement uncertainties with the value of
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0.91 measured by HPLC. Although the SOA yield for the reaction with NO3 radicals is 12%
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larger than for the reaction with OH radicals, the 4NC yield is larger by a factor of 3. This shows
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again that contributions from products other than 4NC comprise a considerable fraction of the
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SOA formed from the OH radical reaction, whereas reaction with NO3 quantitatively produces
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4NC.
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The SOA yield of 1.34 measured here for the OH radical-initiated reaction is much
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higher than the value of 0.53 reported previously by Borrás and Tortajada-Genaro.21 This is most
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likely due to the loss of fewer reaction products to the chamber walls during our 5 min (the time
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that the lights were turned on to create OH radicals) experiments compared to their 7 h
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experiments, and also our use of seed particles, whose surface area enhanced the rate of
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condensation of reaction products to particles and thus reduced loses due to condensation on the
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chamber walls.24,25 The experiments conducted by Borrás and Tortajada-Genaro21 also differed
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from ours in that they allowed O3 to form (by not adding NO), and O3 could compete with OH
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radicals in reactions with catechol.17,18
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ATMOSPHERIC IMPLICATIONS
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The yields of 4NC measured here for the reaction of catechol with OH and NO3 radicals in the presence of NOx have implications for explicit chemical modeling. In MCM v3.1, the
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reaction of catechol with OH radicals is assumed to produce 4NC with unit yield.11 Our results
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suggest, however, that although this is valid for the reaction with NO3 radicals, other products
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are formed in significant yields in the OH radical reaction. Further identification and
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quantification of those products are needed to determine other reaction pathways, with an
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important question being the extent to which abstraction of a phenolic hydrogen competes with
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addition of an OH radical to the aromatic ring.
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By considering various potential loss processes and the properties of 4NC, one can obtain
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a sense of its fate following formation from reaction of catechol with OH or NO3 radicals near a
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wildfire plume. The short atmospheric lifetimes of catechol (estimated above as approximately
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1.4 h and 20 s for reactions with OH and NO3 radicals at global average oxidant concentrations)
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and the high concentrations of NO2 present in the early stages of a wildfire plume suggests rapid
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removal of catechol and rapid 4NC formation close to the wildfire. Although the rate constants
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for reaction of 4NC with OH and NO3 radicals have not been measured, it is known that,
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compared to their unsubstituted aromatic analogs, nitroaromatics react ~30 times more slowly
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with OH radicals49,50 and >100 times more slowly with NO3 radicals.39 Assuming a similar
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relationship for catechol and 4NC, the lifetimes of 4NC with respect to gas-phase reactions with
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OH and NO3 radicals are expected to be about 42 h and 30 min. The overall lifetimes are likely
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to be longer than this, however, since the saturation concentration of 4NC (~13 µg m-3) indicates
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that it should be present in both the gas and organic particle phases in typical ambient
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environments, where organic aerosol loadings are ~1–10 µg m-3,51 with a higher fraction in
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particles near wildfires, where loadings can reach ~100 µg m-3.52 This is consistent with the
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detection of 4NC and its methylated derivatives in aerosol sampled from biomass burning events
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during winter at concentrations of 0.1–100 ng m-3, 53–55 with cold temperatures reducing the
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vapor pressure and enhancing gas-to-particle partitioning of 4NC. Furthermore, although the
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Henry’s Law constant for 4NC has not been reported, by comparing values for phenol, 4-
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nitrophenol, and catechol (2.8 x 103,56 2.1 x 104,56 and 8.3 x 105 mol L-1 atm-1,57 respectively), it
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is expected that the value for 4NC will be at least 106 mol L-1 atm-1. The high water solubility of
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4NC thus allows it to be taken up into aqueous particles,58 which is consistent with its observed
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presence in rainwater.58 Since a considerable fraction of 4NC should be present in the organic
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and aqueous phases of aerosol particles, which will reduce the amount available for removal by
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reaction with OH and NO3 radicals, it is possible that 4NC can undergo long-range transport. It is
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also worth noting that although this study was concerned with gas-phase reactions of catechol,
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uptake into aqueous particles containing dissolved H2O2 and iron can lead to Fenton chemistry,59,
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60
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can occur in the presence and absence of light suggests that there are additional competing
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processes to the gas-phase formation of 4NC from reaction of catechol with OH and NO3
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radicals.
which mainly proceeds by hydroxylation of the ring to produce benzenetriols.59, 60 That this
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The results from this work can also be used to provide insight into the possible
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importance of catechol oxidation to SOA formed from biomass burning emissions. Using the
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SOA yield of 1.34 measured for the reaction of catechol with OH radicals, and an emission ratio
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of 4 mmol catechol mol-1 CO,9,12 we estimate an organic aerosol enhancement of 23 μg m-3
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ppmv-1 CO over background concentrations. It should be emphasized, however, that the emission
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ratio of catechol used in this estimate exhibits large variability between fires, burn conditions,
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and biomass fuel type.9,12 Also, because the dominant OH radical reaction product, 4NC, is
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expected to exist less fully in the particle phase in the atmosphere than in the chamber
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experiments, the SOA yield of 1.34 may be too high. Nonetheless, when compared to POA and
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SOA concentrations reported for biomass burning field campaigns,1 this estimate suggests that
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catechol oxidation alone could account for ~10–40% of the organic aerosol mass (see Figure 1B
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in de Gouw and Jimenez1). This agrees reasonably well with the prediction of Veres et al.,12
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where catechol emission ratios were measured by burning wood in the laboratory. Furthermore,
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in a series of wood burning experiments, Bruns et al.61 measured the amounts of VOCs reacted
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and SOA formed when emissions were reacted with OH radicals generated by photolysis of
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HONO. By multiplying the amount of VOCs reacted by published SOA yields they estimated
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that 22 VOCs could account for 84–116% of measured SOA mass, with 8% being due to
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catechol oxidation. If our measured SOA yield of 1.34 is used instead of the value of 0.39 taken
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from the literature,62 then catechol oxidation would account for 27% of SOA mass. This may be
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a more accurate estimate than that of Bruns et al.,61 since the SOA yield of 0.39 was measured
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for catechol oxidation in the absence of NOx,62 conditions that probably do not represent the
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chemistry that occurred during their HONO photolysis experiments. Finally, the mechanism of formation and optical properties of 4NC, as well as
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methylnitrocatechols, suggests a possible role for these compounds in O3 formation in biomass
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burning plumes. Iinuma et al.53 have shown that methylnitrocatechols are produced from the
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reaction of methylhydroxybenzenes with OH radicals (analogous to formation of 4NC from
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catechol), but with an estimated molar yield in the aerosol of 0.003, and have suggested them as
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aerosol tracers of biomass burning. Nitroaromatic compounds are components of brown carbon63,
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thus attenuate UV light.66 This attenuation, and the removal of NOx by formation of
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nitroaromatics, may play a role in the lack of observed O3 formation in some wildfire plumes.6
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For example, NOx emission ratios average 30 ppbv ppmv-1 CO for pine fuels,67 while catechol
(as shown from the filters in Figure S7 and absorbance measurements by Hinrichs et al.65), and
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emission ratios can vary from 0.2 – 4 ppbv ppmv-1 CO.9,12 When combined with our results of a
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30% yield of 4NC from catechol oxidation by OH in the presence of NOx, this suggests that up
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to 1.2 ppbv [ppmv-1 CO]-1 of NOx could be lost as a result of 4NC formation, representing 4% of
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emitted NOx. The sequestration of NOx can also occur through formation of peroxyacyl nitrates
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that can be efficiently formed from alkenes and acetaldehyde, which are all abundant in wildfire
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smoke.
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ACKNOWLEDGMENTS
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This work was funded by the Department of Energy, Office of Biological and
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Environmental Sciences under Grant DE-SC0010470, and by the National Science Foundation
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under Grant AGS-1420007. Any opinions, findings, and conclusions or recommendations
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expressed in this material are those of the author and do not necessarily reflect the views of the
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National Science Foundation (NSF).
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Table 1: Experimental conditions and yields of SOA and 4NC formed from reactions of catechol (Cat) with OH and NO3 radicals.
481 482
a
483 484 485 486
b
Experiment
Cata (ppb)
∆Cata (ppb)
CH3ONO (ppb)
NO (ppb)
JNO2 (min-1)
N 2O 5 (ppb)
SOA mass yield
4NCb molar yield
Catechol + OH
95 ± 5
57 ± 5
1030
1010
0.14
0
1.40
0.31 ± 0.03
Catechol + OH
670 ± 40
560 ± 40
4940
4980
0.37
0
1.11
0.33 ± 0.03
Catechol + OH
140 ± 20
100 ± 30
4060
4110
0.14
0
1.45
0.28 ± 0.08
Catechol + OH
50 ± 5
29 ± 5
1020
5090
0.37
0
1.38
0.27 ± 0.06
Catechol + NO3
193 ± 8
124 ± 9
0
0
0
320
1.61
0.95 ± 0.08
Catechol + NO3
185 ± 10
150 ± 14
0
0
0
480
1.38
0.86 ± 0.05
Uncertainties for catechol concentrations are standard deviations calculated from the duplicate measurements made before and after reaction. Uncertainties in 4NC yield were calculated by propagation of uncertainties in catechol concentration, flow rates for filter sampling, mass measurements, and the 4NC HPLC calibration curve.
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Figure 1. Real-time TDPBMS mass spectra of SOA formed from reactions of catechol with (A) OH radicals, and (B) NO3 radicals, and (C) aerosol formed from atomization of a 4NC standard. 23
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491 492 493 494 495 496 497
Figure 2. ATR-FTIR spectra of SOA formed from reactions of catechol with (A) OH radicals and (B) NO3 radicals, and (C) a 4NC standard. Wavenumber ranges correspond to the following functional group vibrational modes: O-H stretch (3500 – 3100 cm-1), C-H stretch from DOS (3000-2900 cm-1), carbonyl C=O stretch (1750-1650 cm-1), aromatic C=C stretch (1600 – 1450 cm-1), and nitro N-O stretch (1330 – 1280 cm-1).
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Figure 3. Proposed mechanism for forming 4NC from reactions of catechol with OH or NO3 radicals in air in the presence of NOx.
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SUPPORTING INFORMATION The supporting information contains the following information: HPLC calibration curves of 4NC and 5-nitro-1,2,3-benzenetriol; UV-Vis spectra of 4NC and 5-nitro-1,2,3-benzenetriol; proposed electron ionization mechanism for 4NC; thermal desorption profiles of SOA and 4NC; photograph of SOA collected on Teflon filters; HPLC chromatogram of SOA; CI-ITMS mass spectra of 5-nitro-1,2,3-benzenetriol; HPLC chromatogram of carbonyl derivatized SOA; and references. REFERENCES 1. de Gouw, J. A.; Jimenez, J. L. Organic aerosols in the Earth’s atmosphere. Environ. Sci. Technol. 2009, 43, 7614–7618. 2. Crutzen, P. J.; Andreae, M. O. Biomass burning in the tropics: impact on atmospheric chemistry and biogeochemical cycles. Science 1990, 250, 1669–1678. 3. Val Martin, M.; Logan, J. A.; Kahn, R. A.; Leung, F. -Y.; Nelson, D. L.; Diner, D. J. Smoke injection heights from fires in North America: analysis of 5 years of satellite observations. Atmos. Chem. Phys. 2010, 10, 1491–1510. 4. Ortega, A. M.; Day, D. A.; Cubison, M. J.; Brune, W. H.; Bon, D.; de Gouw, J. A.; Jimenez, J. L. Secondary organic aerosol formation and primary organic aerosol oxidation from biomassburning smoke in a flow reactor during FLAME-3. Atmos. Chem. Phys. 2013, 13, 11551–11571. 5. Hecobian, A.; Liu, Z.; Hennigan, C. J.; Huey, L. G.; Jimenez, J. L.; Cubison, M. J.; Vay, S.; Diskin, G. S.; Sachse, G. W.; Wisthaler, A.; Mikoviny, T.; Weinheimer, A. J.; Liao, J.; Knapp, D. J.; Wennberg, P. O.; Kürten, A.; Crounse, J. D.; St. Clair, J.; Wang, Y.; Weber, R. J. Comparison of chemical characteristics of 495 biomass burning plumes intercepted by the NASA DC-8 aircraft during the ARCTAS/CARB-2008 field campaign. Atmos. Chem. Phys. 2011, 11, 13325—13337. 6. Jaffe, D. A.; Wigder, N. L. Ozone production from wildfires: a critical review. Atmos. Environ. 2012, 51, 1–10. 7. Yokelson, R. J.; Burling, I. R.; Gilman, J. B.; Warneke, C.; Stockwell, C. E.; de Gouw, J.; Akagi, S. K.; Urbanski, S. P.; Veres, P.; Roberts, J. M.; Kuster, W. C.; Reardon, J.; Griffith, D. W. T.; Johnson, T. J.; Hosseini, S.; Miller, J. W.; Cocker III, D. R.; Jung, H.; Weise, D. R. Coupling field and laboratory measurements to estimate the emission factors of identified and unidentified trace gases for prescribed fires. Atmos. Chem. Phys. 2013, 13, 89–116. 8. Stockwell, C. E.; Veres, P. R.; Williams, J.; Yokelson, R. J. Characterization of biomass burning emissions from cooking fires, peat, crop residue, and other fuels with high-resolution proton-transfer-reaction time-of-flight mass spectrometry. Atmos. Chem. Phys. 2015, 15, 845– 865.
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