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An extensive program of experiments focused on biomass burning emissions began with a laboratory phase in which vegetative fuels commonly consumed in prescribed fires were collected in the southeastern and southwestern US and burned in a series of 71 fires at the US Forest Service Fire Sciences Laboratory in Missoula, Montana. The particulate matter (PM2.5) emissions were measured by gravimetric filter sampling with subsequent analysis for elemental carbon (EC), organic carbon (OC), and 38 elements. The trace gas emissions were measured by an open-path Fourier transform infrared (OP-FTIR) spectrometer, proton-transfer-reaction mass spectrometry (PTR-MS), proton-transfer ion-trap mass spectrometry (PIT-MS), negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS), and gas chromatography with MS detection (GC-MS). 204 trace gas species (mostly non-methane organic compounds (NMOC)) were identified and quantified with the above instruments. Many of the 182 species quantified by the GC-MS have rarely, if ever, been measured in smoke before. An additional 153 significant peaks in the unit mass resolution mass spectra were quantified, but either could not be identified or most of the signal at that molecular mass was unaccounted for by identifiable species. In a second, \"field\" phase of this program, airborne and ground-based measurements were made of the emissions from prescribed fires that were mostly located in the same land management units where the fuels for the lab fires were collected. A broad variety, but smaller number of species (21 trace gas species and PM2.5) was measured on 14 fires in chaparral and oak savanna in the southwestern US, as well as pine forest understory in the southeastern US and Sierra Nevada mountains of California. The field measurements of emission factors (EF) are useful both for modeling and to examine the representativeness of our lab fire EF. The lab EF/field EF ratio for the pine understory fuels was not statistically different from one, on average. However, our lab EF for \"smoldering compounds\" emitted from the semiarid shrubland fuels should likely be increased by a factor of ~2.7 to better represent field fires. Based on the lab/field comparison, we present emission factors for 357 pyrogenic species (including unidentified species) for 4 broad fuel types: pine understory, semiarid shrublands, coniferous canopy, and organic soil. To our knowledge this is the most comprehensive measurement of biomass burning emissions to date and it should enable improved representation of smoke composition in atmospheric models. The results support a recent estimate of global NMOC emissions from biomass burning that is much higher than widely used estimates and they provide important insights into the nature of smoke. 31–72% of the mass of gas-phase NMOC species was attributed to species that we could not identify. These unidentified species are not represented in most models, but some provision should be made for the fact that they will react in the atmosphere. In addition, the total mass of gas-phase NMOC divided by the mass of co-emitted PM2.5 averaged about three (range ~2.0–8.7). About 35–64% of the NMOC were likely semivolatile or of intermediate volatility. Thus, the gas-phase NMOC represent a large reservoir of potential precursors for secondary formation of ozone and organic aerosol. For the single lab fire in organic soil about 28% of the emitted carbon was present as gas-phase NMOC and ~72% of the mass of these NMOC was unidentified, highlighting the need to learn more about the emissions from smoldering organic soils. The mass ratio of total NMOC to \"NOx as NO\" ranged from 11 to 267, indicating that NOx-limited O3 production would be common in evolving biomass burning plumes. The fuel consumption per unit area was 7.0 ± 2.3 Mg ha−1 and 7.7 ± 3.7 Mg ha−1 for pine-understory and semiarid shrubland prescribed fires, respectively.

Biomass burning (BB) is a major global source of trace gases and particles. Accurately representing the production and evolution of these emissions is an important goal for atmospheric chemical transport models. We measured a suite of gases and aerosols emitted from an 81 hectare prescribed fire in chaparral fuels on the central coast of California, US on 17 November 2009. We also measured physical and chemical changes that occurred in the isolated downwind plume in the first ~4 h after emission. The measurements were carried out onboard a Twin Otter aircraft outfitted with an airborne Fourier transform infrared spectrometer (AFTIR), aerosol mass spectrometer (AMS), single particle soot photometer (SP2), nephelometer, LiCor CO2 analyzer, a chemiluminescence ozone instrument, and a wing-mounted meteorological probe. Our measurements included: CO2; CO; NOx; NH3; non-methane organic compounds; organic aerosol (OA); inorganic aerosol (nitrate, ammonium, sulfate, and chloride); aerosol light scattering; refractory black carbon (rBC); and ambient temperature, relative humidity, barometric pressure, and three-dimensional wind velocity. The molar ratio of excess O3 to excess CO in the plume (ΔO3/ΔCO) increased from −5.13 (±1.13) × 10−3 to 10.2 (±2.16) × 10−2 in ~4.5 h following smoke emission. Excess acetic and formic acid (normalized to excess CO) increased by factors of 1.73 ± 0.43 and 7.34 ± 3.03 (respectively) over the same time since emission. Based on the rapid decay of C2H4 we infer an in-plume average OH concentration of 5.27 (±0.97) × 106 molec cm−3, consistent with previous studies showing elevated OH concentrations in biomass burning plumes. Ammonium, nitrate, and sulfate all increased over the course of 4 h. The observed ammonium increase was a factor of 3.90 ± 2.93 in about 4 h, but accounted for just ~36% of the gaseous ammonia lost on a molar basis. Some of the gas phase NH3 loss may have been due to condensation on, or formation of, particles below the AMS detection range. NOx was converted to PAN and particle nitrate with PAN production being about two times greater than production of observable nitrate in the first ~4 h following emission. The excess aerosol light scattering in the plume (normalized to excess CO2) increased by a factor of 2.50 ± 0.74 over 4 h. The increase in light scattering was similar to that observed in an earlier study of a biomass burning plume in Mexico where significant secondary formation of OA closely tracked the increase in scattering. In the California plume, however, ΔOA/ΔCO2 decreased sharply for the first hour and then increased slowly with a net decrease of ~20% over 4 h. The fraction of thickly coated rBC particles increased up to ~85% over the 4 h aging period. Decreasing OA accompanied by increased scattering/particle coating in initial aging may be due to a combination of particle coagulation and evaporation processes. Recondensation of species initially evaporated from the particles may have contributed to the subsequent slow rise in OA. We compare our results to observations from other plume aging studies and suggest that differences in environmental factors such as smoke concentration, oxidant concentration, actinic flux, and RH contribute significantly to the variation in plume evolution observations.

Vegetation commonly managed by prescribed burning was collected from five southeastern and southwestern US military bases and burned under controlled conditions at the US Forest Service Fire Sciences Laboratory in Missoula, Montana. The smoke emissions were measured with a large suite of state-of-the-art instrumentation including an open-path Fourier transform infrared (OP-FTIR) spectrometer for measurement of gas-phase species. The OP-FTIR detected and quantified 19 gas-phase species in these fires: CO2, CO, CH4, C2H2, C2H4, C3H6, HCHO, HCOOH, CH3OH, CH3COOH, furan, H2O, NO, NO2, HONO, NH3, HCN, HCl, and SO2. Emission factors for these species are presented for each vegetation type burned. Gas-phase nitrous acid (HONO), an important OH precursor, was detected in the smoke from all fires. The HONO emission factors ranged from 0.15 to 0.60 g kg−1 and were higher for the southeastern fuels. The fire-integrated molar emission ratios of HONO (relative to NOx) ranged from approximately 0.03 to 0.20, with higher values also observed for the southeastern fuels. The majority of non-methane organic compound (NMOC) emissions detected by OP-FTIR were oxygenated volatile organic compounds (OVOCs) with the total identified OVOC emissions constituting 61 ± 12% of the total measured NMOC on a molar basis. These OVOC may undergo photolysis or further oxidation contributing to ozone formation. Elevated amounts of gas-phase HCl and SO2 were also detected during flaming combustion, with the amounts varying greatly depending on location and vegetation type. The fuels with the highest HCl emission factors were all located in the coastal regions, although HCl was also observed from fuels farther inland. Emission factors for HCl were generally higher for the southwestern fuels, particularly those found in the chaparral biome in the coastal regions of California.

Within minutes after emission, complex photochemistry in biomass burning smoke plumes can cause large changes in the concentrations of ozone (O3) and organic aerosol (OA). Being able to understand and simulate this rapid chemical evolution under a wide variety of conditions is a critical part of forecasting the impact of these fires on air quality, atmospheric composition, and climate. Here we use version 2.1 of the Aerosol Simulation Program (ASP) to simulate the evolution of O3 and secondary organic aerosol (SOA) within a young biomass burning smoke plume from the Williams prescribed fire in chaparral, which was sampled over California in November 2009. We demonstrate the use of a method for simultaneously accounting for the impact of the unidentified intermediate volatility, semi-volatile, and extremely low volatility organic compounds (here collectively called \"SVOCs\") on the formation of OA (using the Volatility Basis Set – VBS) and O3 (using the concept of mechanistic reactivity). We show that this method can successfully simulate the observations of O3, OA, NOx, ethylene (C2H4), and OH to within measurement uncertainty using reasonable assumptions about the average chemistry of the unidentified SVOCs. These assumptions were (1) a reaction rate constant with OH of ~ 10-11 cm3 s−1; (2) a significant fraction (up to ~ 50 %) of the RO2 + NO reaction resulted in fragmentation, rather than functionalization, of the parent SVOC; (3) ~ 1.1 molecules of O3 were formed for every molecule of SVOC that reacted; (4) ~ 60 % of the OH that reacted with the unidentified non-methane organic compounds (NMOC) was regenerated as HO2; and (5) that ~ 50 % of the NO that reacted with the SVOC peroxy radicals was lost, presumably to organic nitrate formation. Additional evidence for the fragmentation pathway is provided by the observed rate of formation of acetic acid (CH3COOH), which is consistent with our assumed fragmentation rate. However, the model overestimates peroxyacetyl nitrate (PAN) formation downwind by about 50 %, suggesting the need for further refinements to the chemistry. This method could provide a way for classifying different smoke plume observations in terms of the average chemistry of their SVOCs, and could be used to study how the chemistry of these compounds (and the O3 and OA they form) varies between plumes.

We have measured emission factors for 19 trace gas species and particulate matter (PM2.5) from 14 prescribed fires in chaparral and oak savanna in the southwestern US, as well as conifer forest understory in the southeastern US and Sierra Nevada mountains of California. These are likely the most extensive emission factor field measurements for temperate biomass burning to date and the only published emission factors for temperate oak savanna fuels. This study helps to close the gap in emissions data available for temperate zone fires relative to tropical biomass burning. We present the first field measurements of the biomass burning emissions of glycolaldehyde, a possible precursor for aqueous phase secondary organic aerosol formation. We also measured the emissions of phenol, another aqueous phase secondary organic aerosol precursor. Our data confirm previous observations that urban deposition can impact the NOx emission factors and thus subsequent plume chemistry. For two fires, we measured both the emissions in the convective smoke plume from our airborne platform and the unlofted residual smoldering combustion emissions with our ground-based platform. The smoke from residual smoldering combustion was characterized by emission factors for hydrocarbon and oxygenated organic species that were up to ten times higher than in the lofted plume, including high 1,3-butadiene and isoprene concentrations which were not observed in the lofted plume. This should be considered in modeling the air quality impacts for smoke that disperses at ground level. We also show that the often ignored unlofted emissions can significantly impact estimates of total emissions. Preliminary evidence suggests large emissions of monoterpenes in the residual smoldering smoke. These data should lead to an improved capacity to model the impacts of biomass burning in similar temperate ecosystems.

We report trace-gas emission factors from three pine-understory prescribed fires in South Carolina, US measured during the fall of 2011. The fires were more intense than many prescribed burns because the fuels included mature pine stands not subjected to prescribed fire in decades that were lit following an extended drought. Emission factors were measured with a fixed open-path Fourier transform infrared (OP-FTIR) system that was deployed on the fire control lines. We compare these emission factors to those measured with a roving, point sampling, land-based FTIR and an airborne FTIR deployed on the same fires. We also compare to emission factors measured by a similar OP-FTIR system deployed on savanna fires in Africa. The data suggest that the method used to sample smoke can strongly influence the relative abundance of the emissions that are observed. The majority of fire emissions were lofted in the convection column and were sampled by the airborne FTIR. The roving, ground-based, point sampling FTIR measured the contribution of individual residual smoldering combustion fuel elements scattered throughout the burn site. The OP-FTIR provided a ~ 30 m path-integrated sample of emissions transported to the fixed path via complex ground-level circulation. The OP-FTIR typically probed two distinct combustion regimes, \"flaming-like\" (immediately after adjacent ignition and before the adjacent plume achieved significant vertical development) and \"smoldering-like.\" These two regimes are denoted \"early\" and \"late\", respectively. The path-integrated sample of the ground-level smoke layer adjacent to the fire from the OP-FTIR provided our best estimate of fire-line exposure to smoke for wildland fire personnel. We provide a table of estimated fire-line exposures for numerous known air toxics based on synthesizing results from several studies. Our data suggest that peak exposures are more likely to challenge permissible exposure limits for wildland fire personnel than shift-average (8 h) exposures.

In October-November 2011 we measured trace gas emission factors from seven prescribed fires in South Carolina (SC), US, using two Fourier transform infrared spectrometer (FTIR) systems and whole air sampling (WAS) into canisters followed by gas-chromatographic analysis. A total of 97 trace gas species were quantified from both airborne and ground-based sampling platforms, making this one of the most detailed field studies of fire emissions to date. The measurements include the first emission factors for a suite of monoterpenes produced by heating vegetative fuels during field fires. The first quantitative FTIR observations of limonene in smoke are reported along with an expanded suite of monoterpenes measured by WAS including α-pinene, β-pinene, limonene, camphene, 4-carene, and myrcene. The known chemistry of the monoterpenes and their measured abundance of 0.4-27.9% of non-methane organic compounds (NMOCs) and ~ 21% of organic aerosol (mass basis) suggests that they impacted secondary formation of ozone (O3 ), aerosols, and small organic trace gases such as methanol and formaldehyde in the sampled plumes in the first few hours after emission. The variability in the initial terpene emissions in the SC fire plumes was high and, in general, the speciation of the initially emitted gas-phase NMOCs was 13-195% different from that observed in a similar study in nominally similar pine forests in North Carolina ~ 20 months earlier. It is likely that differences in stand structure and environmental conditions contributed to the high variability observed within and between these studies. Similar factors may explain much of the variability in initial emissions in the literature. The δHCN/δCO emission ratio, however, was found to be fairly consistent with previous airborne fire measurements in other coniferous-dominated ecosystems, with the mean for these studies being 0.90 ± 0.06%, further confirming the value of HCN as a biomass burning tracer. The SC results also support an earlier finding that C3 -C4 alkynes may be of use as biomass burning indicators on the time-scale of hours to a day. It was possible to measure the downwind chemical evolution of the plume on four of the fires and significant O3 formation (δO3 /δCO from 10-90%) occurred in all of these plumes within two hours. The slowest O3 production was observed on a cloudy day with low co-emission of NOx . The fastest O3 production was observed on a sunny day when the downwind plume almost certainly incorporated significant additional NOx by passing over the Columbia, SC metropolitan area. Due to rapid plume dilution, it was only possible to acquire high-quality downwind data for two other trace gas species (formaldehyde and methanol) during two of the fires. In all four of these cases, significant increases in formaldehyde and methanol were observed in <2 h. This is likely the first direct observation of post-emission methanol production in biomass burning plumes. Post-emission production of methanol does not always happen in young biomass burning plumes, and its occurrence in this study could have involved terpene precursors to a significant extent.

In October–November 2011 we measured trace gas emission factors from seven prescribed fires in South Carolina (SC), US, using two Fourier transform infrared spectrometer (FTIR) systems and whole air sampling (WAS) into canisters followed by gas-chromatographic analysis. A total of 97 trace gas species were quantified from both airborne and ground-based sampling platforms, making this one of the most detailed field studies of fire emissions to date. The measurements include the first emission factors for a suite of monoterpenes produced by heating vegetative fuels during field fires. The first quantitative FTIR observations of limonene in smoke are reported along with an expanded suite of monoterpenes measured by WAS including α-pinene, β-pinene, limonene, camphene, 4-carene, and myrcene. The known chemistry of the monoterpenes and their measured abundance of 0.4–27.9% of non-methane organic compounds (NMOCs) and ~ 21% of organic aerosol (mass basis) suggests that they impacted secondary formation of ozone (O3), aerosols, and small organic trace gases such as methanol and formaldehyde in the sampled plumes in the first few hours after emission. The variability in the initial terpene emissions in the SC fire plumes was high and, in general, the speciation of the initially emitted gas-phase NMOCs was 13–195% different from that observed in a similar study in nominally similar pine forests in North Carolina ~ 20 months earlier. It is likely that differences in stand structure and environmental conditions contributed to the high variability observed within and between these studies. Similar factors may explain much of the variability in initial emissions in the literature. The ΔHCN/ΔCO emission ratio, however, was found to be fairly consistent with previous airborne fire measurements in other coniferous-dominated ecosystems, with the mean for these studies being 0.90 ± 0.06%, further confirming the value of HCN as a biomass burning tracer. The SC results also support an earlier finding that C3-C4 alkynes may be of use as biomass burning indicators on the time-scale of hours to a day. It was possible to measure the downwind chemical evolution of the plume on four of the fires and significant O3 formation (ΔO3/ΔCO from 10–90%) occurred in all of these plumes within two hours. The slowest O3 production was observed on a cloudy day with low co-emission of NOx. The fastest O3 production was observed on a sunny day when the downwind plume almost certainly incorporated significant additional NOx by passing over the Columbia, SC metropolitan area. Due to rapid plume dilution, it was only possible to acquire high-quality downwind data for two other trace gas species (formaldehyde and methanol) during two of the fires. In all four of these cases, significant increases in formaldehyde and methanol were observed in <2 h. This is likely the first direct observation of post-emission methanol production in biomass burning plumes. Post-emission production of methanol does not always happen in young biomass burning plumes, and its occurrence in this study could have involved terpene precursors to a significant extent.

In this study we identify pyrolysis gases from prescribed burns conducted in pine forests with a shrub understory captured using a manual extraction device. The device selectively sampled emissions ahead of the flame front, minimizing the collection of oxidized gases, with the captured gases analyzed in the laboratory using infrared (IR) absorption spectroscopy. Results show that emission ratios (ERs) relative to CO for ethene and acetylene were significantly greater than in previous fire studies, suggesting that the sample device was able to collect gases predominantly generated prior to ignition. Further evidence that ignition had not begun was corroborated by novel IR detections of several species, in particular naphthalene. With regards to oxygenated species, several aldehydes (acrolein, furaldehyde, acetaldehyde, formaldehyde) and carboxylic acids (formic, acetic) were all observed; results show that ERs for acetaldehyde were noticeably greater, while ERs for formaldehyde and acetic acid were lower compared to other studies. The acetylene-to-furan ratio also suggests that high-temperature pyrolysis was the dominant process generating the collected gases.