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Data from both laboratory studies and atmospheric measurements are used to develop an empirical parameterization for the immersion freezing activity of natural mineral dust particles. Measurements made with the Colorado State University (CSU) continuous flow diffusion chamber (CFDC) when processing mineral dust aerosols at a nominal 105% relative humidity with respect to water (RHw) are taken as a measure of the immersion freezing nucleation activity of particles. Ice active frozen fractions vs. temperature for dusts representative of Saharan and Asian desert sources were consistent with similar measurements in atmospheric dust plumes for a limited set of comparisons available. The parameterization developed follows the form of one suggested previously for atmospheric particles of non-specific composition in quantifying ice nucleating particle concentrations as functions of temperature and the total number concentration of particles larger than 0.5 μm diameter. Such an approach does not explicitly account for surface area and time dependencies for ice nucleation, but sufficiently encapsulates the activation properties for potential use in regional and global modeling simulations, and possible application in developing remote sensing retrievals for ice nucleating particles. A calibration factor is introduced to account for the apparent underestimate (by approximately 3, on average) of the immersion freezing fraction of mineral dust particles for CSU CFDC data processed at an RHw of 105% vs. maximum fractions active at higher RHw. Instrumental factors that affect activation behavior vs. RHw in CFDC instruments remain to be fully explored in future studies. Nevertheless, the use of this calibration factor is supported by comparison to ice activation data obtained for the same aerosols from Aerosol Interactions and Dynamics of the Atmosphere (AIDA) expansion chamber cloud parcel experiments. Further comparison of the new parameterization, including calibration correction, to predictions of the immersion freezing surface active site density parameterization for mineral dust particles, developed separately from AIDA experimental data alone, shows excellent agreement for data collected in a descent through a Saharan aerosol layer. These studies support the utility of laboratory measurements to obtain atmospherically relevant data on the ice nucleation properties of dust and other particle types, and suggest the suitability of considering all mineral dust as a single type of ice nucleating particle as a useful first-order approximation in numerical modeling investigations.

Experiments were conducted to investigate light absorption of organic aerosol (OA) in fresh and photo-chemically aged biomass-burning emissions. The experiments considered residential hardwood fuel (oak) and fuels commonly consumed in wild-land and prescribed fires in the United States (pocosin pine and gallberry). Photo-chemical aging was performed in an environmental chamber. We constrained the effective light-absorption properties of the OA using conservative limiting assumptions, and found that both primary organic aerosol (POA) in the fresh emissions and secondary organic aerosol (SOA) produced by photo-chemical aging contain brown carbon, and absorb light to a significant extent. This work presents the first direct evidence that SOA produced in aged biomass-burning emissions is absorptive. For the investigated fuels, SOA is less absorptive than POA in the long visible, but exhibits stronger wavelength-dependence and is more absorptive in the short visible and near-UV. Light absorption by SOA in biomass-burning emissions might be an important contributor to the global radiative forcing budget.

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.

Open biomass burning is a significant source of primary air pollutants such as particulate matter (PM) and non-methane organic gases (NMOG). However, the physical and chemical atmospheric processing of these emissions during transport is poorly understood. Atmospheric transformations of biomass burning emissions have been investigated in environmental chambers, but there have been limited opportunities to investigate these transformations in the atmosphere. In this study, we deployed a suite of real-time instrumentation on a Twin Otter aircraft to sample smoke from prescribed fires in South Carolina, conducting measurements at both the source and downwind to characterize smoke evolution with atmospheric aging. Organic aerosol (OA) within the smoke plumes was quantified using an aerosol mass spectrometer (AMS); refractory black carbon (rBC) was quantified using a single-particle soot photometer, and carbon monoxide (CO) and carbon dioxide (CO2) were measured using a cavity ring-down spectrometer. During the two fires for which we were able to obtain aerosol aging data, normalized excess mixing ratios and \"export factors\" of conserved species (rBC, CO, CO2) suggested that changes in emissions at the source did not account for most of the differences observed in samples of increasing age. An investigation of AMS mass fragments indicated that the in-plume fractional contribution (fm/z) to OA of the primary fragment (m/z 60) decreased downwind, while the fractional contribution of the secondary fragment (m/z 44) increased. Increases in f44 are typically interpreted as indicating chemical aging of OA. Likewise, we observed an increase in the O : C elemental ratio downwind, which is usually associated with aerosol aging. However, the rapid mixing of these plumes into the background air suggests that these chemical transformations may be attributable to the different volatilities of the compounds that fragment to these m/z in the AMS. The gas–particle partitioning behavior of the bulk OA observed during the study was consistent with the predictions from a parameterization developed for open biomass burning emissions in the laboratory. Furthermore, we observed no statistically significant increase in total organic mass with atmospheric transport. Hence, our results suggest that dilution-driven evaporation likely dominated over the chemical production of secondary organic aerosol (SOA) within our smoke plumes, presumably due to the fast dilution and limited aging times (< ~ 5 h) that we could sample.

The Mexico City metropolitan area (MCMA) is a region that continues to grow in population and vehicular traffic as well as being the largest source of short-lived climate pollutants (SLCP) in Latin America. The local city government has made significant progress in controlling some of these pollutants, i.e., ozone (O3) and carbon monoxide (CO), but particulate matter (PM2.5 and PM10) and black carbon (BC) have shown a less positive response to mitigation strategies that have been in place for almost 3 decades. For the first time, extended measurements of equivalent black carbon (eBC), derived from light absorption measurements, have been made using a Photoacoustic Extinctiometer (PAX) over a 13 month period from March 2013 through March 2014. The daily trends in workdays (Monday through Saturday) and Sunday eBC, PM2.5 and the co-pollutants CO, O3 and NOx are evaluated with respect to the three primary seasons in the MCMA: rainy, cold and dry and warm and dry. The maximum values in all of the particle and gas concentrations were significantly larger (Student's t test, P < 0.05) during the dry periods than in the rainy season. The changes from rainy to dry seasons for eBC, PM2.5, CO, O3 and NOx were 8.8 to 13.1 μg m−3 (40 %), 49 to 73 μg m−3 (40 %), 2.5 to 3.8 ppm (40 %), 73 to 100 ppb (30 %) and 144 to 252 ppb (53 %), respectively. The primary factors that lead to these large changes between the wet and dry seasons are the accelerated vertical mixing of boundary layer and free tropospheric air by the formation of clouds that dilutes the concentration of the SLCPs, the decreased actinic flux that reduces the production of ozone by photochemical reactions and the heavy, almost daily rain that removes particulate matter. A significant \"weekend effect\" was also identified, particularly the decrease in BC due to fewer large transport vehicles that are fueled by diesel, which produces a large fraction of the BC. The other co-pollutant concentrations are also significantly less on weekends except for O3 that shows no change in maximum values from workdays to Sundays. This lack of change is a result of the balancing effects of lower precursor gases, i.e., VOCs, offset by lower concentrations of NOx, that is an O3 inhibitor. A comparison of the average maximum value of eBC measured during the 1 year period of the current study, with maximum values measured in shorter field campaigns in 2000 and 2006, shows no significant change in the eBC emissions over a 14 year period. This suggests that new methods may need to be developed that can decrease potentially toxic levels of this particulate pollutant.

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.

During the Fire Laboratory at Missoula Experiments (FLAME), we studied the physical, chemical, and optical properties of biomass burning smoke from the laboratory combustion of various wildland fuels. A good understanding of these properties is important in determining the radiative effects of biomass burning aerosols, with impacts on both local and regional visibility and global climate. We measured aerosol size distributions with two instruments: a differential mobility particle sizer (DMPS) and an optical particle counter (OPC). Volume size distributions from different burns varied from monomodal to multimodal, with geometric mean diameters ranging from 0.20–0.57 μm and geometric standard deviations ranging from 1.68–2.97. By reconciling the differences between the two sizing instruments, we estimated aerosol effective refractive indices with values ranging from 1.41 to 1.61. We reconstructed aerosol chemical composition for each burn using data from filters collected and analyzed with the Interagency Monitoring of Protected Visual Environments (IMPROVE) samplers and protocols. Aerosols were generally comprised of carbon with organic species accounting for the largest mass fraction in most cases. We used composition data to calculate aerosol density, which ranged from 1.22–1.92 g cm−3, and real and imaginary refractive indices, which had ranges of 1.55–1.80 and 0.01–0.50 respectively. Aerosol physical, chemical, and optical characterizations were combined to calculate dry mass scattering (MSE) and absorption (MAE) efficiencies at 532 nm. These parameters had values between 1.6–5.7 m2 g−1 and 0.04–0.94 m2 g−1.

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.

Smog chamber experiments were conducted to investigate the chemical and physical transformations of organic aerosol (OA) during photo-oxidation of open biomass burning emissions. The experiments were carried out at the US Forest Service Fire Science Laboratory as part of the third Fire Lab at Missoula Experiment (FLAME III). We investigated emissions from 12 different fuels commonly burned in North American wildfires. The experiments feature atmospheric and plume aerosol and oxidant concentrations; aging times ranged from 3 to 4.5 h. OA production, expressed as a mass enhancement ratio (ratio of OA to primary OA (POA) mass), was highly variable. OA mass enhancement ratios ranged from 2.9 in experiments where secondary OA (SOA) production nearly tripled the POA concentration to 0.7 in experiments where photo-oxidation resulted in a 30 % loss of the OA mass. The campaign-average OA mass enhancement ratio was 1.7 ± 0.7 (mean ± 1σ); therefore, on average, there was substantial SOA production. In every experiment, the OA was chemically transformed. Even in experiments with net loss of OA mass, the OA became increasingly oxygenated and less volatile with aging, indicating that photo-oxidation transformed the POA emissions. Levoglucosan concentrations were also substantially reduced with photo-oxidation. The transformations of POA were extensive; using levoglucosan as a tracer for POA, unreacted POA only contributed 17 % of the campaign-average OA mass after 3.5 h of exposure to typical atmospheric hydroxyl radical (OH) levels. Heterogeneous reactions with OH could account for less than half of this transformation, implying that the coupled gas-particle partitioning and reaction of semi-volatile vapors is an important and potentially dominant mechanism for POA processing. Overall, the results illustrate that biomass burning emissions are subject to extensive chemical processing in the atmosphere, and the timescale for these transformations is rapid.

Black carbon (BC) is a short term climate forcer that directly warms the atmosphere, slows convection, and hinders quantification of the effect of greenhouse gases on climate change. The atmospheric lifetime of BC particles with respect to nucleation scavenging in clouds is controlled by their ability to serve as cloud condensation nuclei (CCN). To serve as CCN under typical conditions, hydrophobic BC particles must acquire hygroscopic coatings. However, the quantitative relationship between coatings and hygroscopic properties for ambient BC particles is not known nor is the time scale for hydrophobic-to-hydrophilic conversion. Here we introduce a method for measuring the hygroscopicity of externally and internally mixed BC particles by coupling a single particle soot photometer with a humidified tandem differential mobility analyzer. We test this technique using uncoated and coated laboratory generated model BC compounds and apply it to characterize the hygroscopicity distribution of ambient BC particles. From these data we derive that the observed number fraction of BC that is CCN active at 0.2 % supersaturation is generally low in an urban area near sources and that it varies with the trajectory of the airmass. We anticipate that our method can be combined with measures of air parcel physical and photochemical age to provide the first quantitative estimates for characterizing hydrophobic-to-hydrophilic conversion rates in the atmosphere.