Biomass burning is a significant source of carbonaceous aerosol in many regions of the world. When present, biomass burning particles may affect the microphysical properties of clouds through their ability to function as cloud condensation nuclei or ice nuclei. We report on measurements of the ice nucleation ability of biomass burning particles performed on laboratory‐generated aerosols at the second Fire Lab at Missoula Experiment. During the experiment we generated smoke through controlled burns of 21 biomass fuels from the United States and Asia. Using a Colorado State University continuous flow diffusion chamber, we measured the condensation/immersion freezing potential at temperatures relevant to cold cumulus clouds (−30°C). Smokes from 9 of the 21 fuels acted as ice nuclei at fractions of 1:10,000 to 1:100 particles in at least one burn of each fuel; emissions from the remaining fuels were below the ice nuclei detection limit for all burns of each fuel. Using a bottom‐up emission model, we estimate that smokes that emit ice nuclei fractions exceeding 1:10,000 particles can perturb ice nuclei concentrations on a regional scale.

[1] In order to understand and predict the role of organic particles in the atmosphere their deliquescence behavior must be understood. Using an optical microscope coupled to a flow cell, we investigated the deliquescence of malonic, succinic, glutaric, and adipic acid particles with sizes ranging from 2 to 40 mm. Deliquescence relative humidities were determined for temperatures ranging from 293 to 243 K. Over this temperature range both succinic acid and adipic acid deliquesced at approximately 100% relative humidity, whereas malonic acid and glutaric acid deliquesced at significantly lower relative humidities. These results are generally in good agreement with previous studies and are within 3% of calculations based on the UNIQUAC (universal quasi-chemical) Functional Group Activity Coefficients (UNIFAC) model and recently published interaction parameters. Our studies also include measurements at temperatures below the eutectic temperatures. At these temperatures, ice did not nucleate; rather the particles underwent deliquescence to form metastable solution droplets. This indicates that solid dicarboxylic acids are not good ice nuclei above 243 K and hence will probably not play a role in ice cloud formation at these temperatures.

The deliquescence and crystallization of ammonium sulfate particles internally mixed with water-soluble organic material have been studied, restricted to an organic mass fraction of less than 0.6. The organic species used were malonic acid, glycerol, levoglucosan (1,6-anhydro-β-d-glucopyranose), and Suwannee River fulvic acid. Our deliquescence results for systems with malonic acid and fulvic acid are in agreement with existing literature values. Glycerol deliquescence results are slightly lower than previous measurements. The levoglucosan results are the first of this kind. Total deliquescence relative humidities for the different systems are the same within the uncertainty of the measurements when the organic mole fraction is less than approximately 0.35. At an organic mole fraction of 0.6, the maximum deviation of total deliquescence relative humidities between the systems is approximately 10% relative humidity. We show that thermodynamic calculations based on a simplified version of a model recently proposed by Clegg et al. (J. Aerosol Sci. 2001, 32, 713) are in agreement with measured values of deliquescence relative humidity up to an organic mole fraction of approximately 0.4 for most of the systems studied. The crystallization relative humidity (CRH) of mixed systems of ammonium sulfate with malonic acid, glycerol, or levoglucosan decreases significantly from the CRH of pure ammonium sulfate when the organic mole fraction is greater than about 0.25. This is in contrast to our previous study with glutaric acid where CRH remained close to CRH of pure ammonium sulfate up to a glutaric acid mole fraction of 0.4. CRH values are shown to vary depending on the type of organic present. In terms of atmospheric implications, we estimate that organics, on average, are only a minor perturbation on the deliquescence relative humidity of the pure inorganic particles, whereas the organics, on average, may decrease the CRH of pure inorganic particles significantly and this effect depends on the type of organic material.

Using optical microscopy, we investigated the crystallization of aqueous ammonium sulfate droplets containing soot and kaolinite, as well as the crystallization of aqueous ammonium sulfate droplets free of solid material. Our results show that soot did not influence the crystallization RH of aqueous ammonium sulfate particles under our experimental conditions. In contrast, kaolinite increased the crystallization RH of the aqueous ammonium sulfate droplets by approximately 10%. In addition, our results show that the crystallization RH of aqueous ammonium sulfate droplets free of solid material does not depend strongly on particle size. This is consistent with conclusions made previously in the literature, based on comparisons of results from different laboratories. From the crystallization results we determined the homogeneous nucleation rates of crystalline ammonium sulfate in aqueous ammonium sulfate droplets and the heterogeneous nucleation rates of crystalline ammonium sulfate in aqueous ammonium sulfate particles containing kaolinite. Using classical nucleation theory and our experimental data, we determined that the interfacial tension between an ammonium sulfate critical nucleus and an aqueous ammonium sulfate solution is 0.064 +/- 0.003 J m(-2) (in agreement with our previous measurements), and the contact angle between an ammonium sulfate critical nucleus and a kaolinite surface is 59 +/- 2 degrees. On the basis of our results, we argue that soot will not influence the crystallization RH of aqueous ammonium sulfate droplets in the atmosphere, but kaolinite can significantly modify the crystallization RH of atmospheric ammonium sulfate droplets. As an example, the CRH50 (the relative humidity at which 50% of the droplets crystallize) ranges from about 41 to 51% RH when the diameter of the kaolinite inclusion ranges from 0.1 to 5 microm. For comparison, the CRH50 of aqueous ammonium sulfate droplets (0.5 microm diameter) free of solid material is approximately 34.3% RH under atmospheric conditions.