Ice nucleating particles (INPs) are vital for ice initiation in, and precipitation from, mixed-phase clouds. A source of INPs from oceans within sea spray aerosol (SSA) emissions has been suggested in previous studies but remained unconfirmed. Here, we show that INPs are emitted using real wave breaking in a laboratory flume to produce SSA. The number concentrations of INPs from laboratory-generated SSA, when normalized to typical total aerosol number concentrations in the marine boundary layer, agree well with measurements from diverse regions over the oceans. Data in the present study are also in accord with previously published INP measurements made over remote ocean regions. INP number concentrations active within liquid water droplets increase exponentially in number with a decrease in temperature below 0 °C, averaging an order of magnitude increase per 5 °C interval. The plausibility of a strong increase in SSA INP emissions in association with phytoplankton blooms is also shown in laboratory simulations. Nevertheless, INP number concentrations, or active site densities approximated using “dry” geometric SSA surface areas, are a few orders of magnitude lower than corresponding concentrations or site densities in the surface boundary layer over continental regions. These findings have important implications for cloud radiative forcing and precipitation within low-level and midlevel marine clouds unaffected by continental INP sources, such as may occur over the Southern Ocean.

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 (RH_w) 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 RH_w of 105% vs. maximum fractions active at higher RH_w. Instrumental factors that affect activation behavior vs. RH_w 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.

We characterized the gas‐ and speciated aerosol‐phase emissions from the open combustion of 33 different plant species during a series of 255 controlled laboratory burns during the Fire Laboratory at Missoula Experiments (FLAME). The plant species we tested were chosen to improve the existing database for U.S. domestic fuels: laboratory‐based emission factors have not previously been reported for many commonly burned species that are frequently consumed by fires near populated regions and protected scenic areas. The plants we tested included the chaparral species chamise, manzanita, and ceanothus, and species common to the southeastern United States (common reed, hickory, kudzu, needlegrass rush, rhododendron, cord grass, sawgrass, titi, and wax myrtle). Fire‐integrated emission factors for gas‐phase CO₂, CO, CH₄, C_2–4hydrocarbons, NH₃, SO₂, NO, NO₂, HNO₃, and particle‐phase organic carbon (OC), elemental carbon (EC), SO₄²⁻, NO₃⁻, Cl⁻, Na⁺, K⁺, and NH₄⁺generally varied with both fuel type and with the fire‐integrated modified combustion efficiency (MCE), a measure of the relative importance of flaming‐ and smoldering‐phase combustion to the total emissions during the burn. Chaparral fuels tended to emit less particulate OC per unit mass of dry fuel than did other fuel types, whereas southeastern species had some of the largest observed emission factors for total fine particulate matter. Our measurements spanned a larger range of MCE than prior studies, and thus help to improve estimates of the variation of emissions with combustion conditions for individual fuels.

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; NO_x; 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. NO_x 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.

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.