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 (PM_2.5) 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 PM_2.5) 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 PM_2.5 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 "NO_x as NO" ranged from 11 to 267, indicating that NO_x-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.

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 NO_x. The fastest O₃ production was observed on a sunny day when the downwind plume almost certainly incorporated significant additional NO_x 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.

Current fire models are designed to model the spread of a linear fire front in dead, small-diameter fuels. Fires in predominantly living vegetation account for a large proportion of annual burned area in the United States. Prescribed burning is used to manage living fuels; however, prescribed burning is currently conducted under conditions that result in marginal burning. We do not understand quantitatively the relative importance of the fuel and environmental variables that determine spread in live vegetation. To address these weaknesses, laboratory fires have been burned to determine the effects of wind, slope, moisture content and fuel characteristics on fire spread in fuel beds of common chaparral species. Four species (Adenostoma fasciculatum, Ceanothus crassifolius, Quercus berberidifolia, Arctostaphylos parryana), two wind velocities (0 and 2 m s−1) and two fuel bed depths (20 and 40 cm) were used. Oven-dry moisture content of fine fuels (<0.63 cm diameter) ranged from 0.09 to 1.06. Seventy of 125 fires successfully propagated the length (2.0 m) of the elevated fuel bed. A logistic model to predict the probability of successful fire spread was developed using stepwise logistic regression. The variables selected to predict propagation were wind velocity, slope percent, moisture content, fuel loading, species and air temperature. Air temperature and species terms were removed from the model for parsimony. The final model correctly classified 94% of the observations. Comparison of results with an empirical decision matrix for prescribed burning in chaparral suggested some agreement between the laboratory data and the empirical tool.

The flammability of living vegetation is influenced by a variety of factors, including moisture content, physical structure and chemical composition. The relative flammability of ornamental vegetation is of interest to homeowners seeking to make their homes ‘fire safe’. The relative importance of the factors influencing fire behaviour characteristics, such as flammability, is unknown. In the present study, oxygen consumption calorimetry was used to obtain selected combustion characteristics of ornamental vegetation. Peak heat release rate, mass loss rate, time to ignition and effective heat of combustion of 100 × 100-mm samples of foliage and small branches were measured using a bench-scale cone calorimeter. Green and oven-dry samples of 10 species were collected and tested seasonally for a period of 1 year. Similar measurements were made on whole shrubs in an intermediate-scale calorimeter. The range of cone calorimeter peak heat release rates for green and oven-dry samples was 1–176 and 49–331 kW m−2, respectively. Moisture content significantly reduced heat release rates and increased time to ignition. Peak heat release rates for Olea europea and Adenostoma fasciculatum were consistently highest over the year of testing; Aloe sp. consistently had the lowest heat release rate. The correlation of peak heat release rates measured by the cone calorimeter and an intermediate-scale calorimeter was statistically significant yet low (0.51). The use of the cone calorimeter as a tool to establish the relative flammability rating for landscape vegetation requires additional investigation.

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.

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, NO_x, 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.