Missed Evaporation from Atmospherically Relevant Inorganic Mixtures Confounds Experimental Aerosol Studies.

Sea salt aerosol particles are highly abundant in the atmosphere and play important roles in the global radiative balance. After influence from continental air, they are typically composed of Na+, Cl-, NH4+, and SO42- and organics. Analogous particle systems are often studied in laboratory settings by atomizing and drying particles from a solution. Here, we present evidence that such laboratory studies may be consistently biased in that they neglect losses of solutes to the gas phase. We present experimental evidence from a hygroscopic tandem differential mobility analyzer and an aerosol mass spectrometer, further supported by thermodynamic modeling. We show that, at normally prevailing laboratory aerosol mass concentrations, for mixtures of NaCl and (NH4)2SO4, a significant portion of the Cl- and NH4+ ions are lost to the gas phase, in some cases, leaving mainly Na2SO4 in the dry particles. Not considering losses of solutes to the gas phase during experimental studies will likely result in misinterpretation of the data. One example of such data is that from particle water uptake experiments. This may bias the explanatory models constructed from the data and introduce errors inte predictions made by air quality or climate models.

Using Novel Molecular-Level Chemical Composition Observations of High Arctic Organic Aerosol for Predictions of Cloud Condensation Nuclei.

Predictions of cloud droplet activation in the late summertime (September) central Arctic Ocean are made using κ-Köhler theory with novel observations of the aerosol chemical composition from a high-resolution time-of-flight chemical ionization mass spectrometer with a filter inlet for gases and aerosols (FIGAERO-CIMS) and an aerosol mass spectrometer (AMS), deployed during the Arctic Ocean 2018 expedition onboard the Swedish icebreaker Oden. We find that the hygroscopicity parameter κ of the total aerosol is 0.39 ± 0.19 (mean ± std). The predicted activation diameter of ∼25 to 130 nm particles is overestimated by 5%, leading to an underestimation of the cloud condensation nuclei (CCN) number concentration by 4-8%. From this, we conclude that the aerosol in the High Arctic late summer is acidic and therefore highly cloud active, with a substantial CCN contribution from Aitken mode particles. Variability in the predicted activation diameter is addressed mainly as a result of uncertainties in the aerosol size distribution measurements. The organic κ was on average 0.13, close to the commonly assumed κ of 0.1, and therefore did not significantly influence the predictions. These conclusions are supported by laboratory experiments of the activation potential of seven organic compounds selected as representative of the measured aerosol.

Effective density and mixing state of aerosol particles in a near-traffic urban environment.

In urban environments, airborne particles are continuously emitted, followed by atmospheric aging. Also, particles emitted elsewhere, transported by winds, contribute to the urban aerosol. We studied the effective density (mass-mobility relationship) and mixing state with respect to the density of particles in central Copenhagen, in wintertime. The results are related to particle origin, morphology, and aging. Using a differential mobility analyzer-aerosol particle mass analyzer (DMA-APM), we determined that particles in the diameter range of 50-400 nm were of two groups: porous soot aggregates and more dense particles. Both groups were present at each size in varying proportions. Two types of temporal variability in the relative number fraction of the two groups were found: soot correlated with intense traffic in a diel pattern and dense particles increased during episodes with long-range transport from polluted continental areas. The effective density of each group was relatively stable over time, especially of the soot aggregates, which had effective densities similar to those observed in laboratory studies of fresh diesel exhaust emissions. When heated to 300 °C, the soot aggregate volatile mass fraction was ∼10%. For the dense particles, the volatile mass fraction varied from ∼80% to nearly 100%.

Volatility of organic aerosol: evaporation of ammonium sulfate/succinic acid aqueous solution droplets.

Condensation and evaporation modify the properties and effects of atmospheric aerosol particles. We studied the evaporation of aqueous succinic acid and succinic acid/ammonium sulfate droplets to obtain insights on the effect of ammonium sulfate on the gas/particle partitioning of atmospheric organic acids. Droplet evaporation in a laminar flow tube was measured in a Tandem Differential Mobility Analyzer setup. A wide range of droplet compositions was investigated, and for some of the experiments the composition was tracked using an Aerosol Mass Spectrometer. The measured evaporation was compared to model predictions where the ammonium sulfate was assumed not to directly affect succinic acid evaporation. The model captured the evaporation rates for droplets with large organic content but overestimated the droplet size change when the molar concentration of succinic acid was similar to or lower than that of ammonium sulfate, suggesting that ammonium sulfate enhances the partitioning of dicarboxylic acids to aqueous particles more than currently expected from simple mixture thermodynamics. If extrapolated to the real atmosphere, these results imply enhanced partitioning of secondary organic compounds to particulate phase in environments dominated by inorganic aerosol.