Facile Method for Determining the Aspect Ratios of Mineral Dust Aerosol by Electron Microscopy

<div><p>Mineral dust is the second largest atmospheric emission by mass and one of the least understood sources. The shape of the particles depends on their composition and has implications for particle optical properties and reactive surface area. Mineral dust particles are often approximated as spheroids to model their optical properties. In this study, scanning electron microscopy (SEM) is used to measure the aspect ratios of calcite, quartz, NX-illite, kaolinite (KGa-1b and KGa-2), and montmorillonite (STx-1b and SWy-2). In addition to traditional SEM images of the top of the particles, the SEM substrates are oriented approximately normal to the electron beam in order to image the side of the particles. In this manner, aspect ratios for the top and side orientation of the particles are determined. Calcite particles have an aspect ratio of approximately 1.3 in both orientations, while quartz particles have an aspect ratio of 1.38 in the top orientation and 1.64 in the side orientation. The clay minerals studied all exhibited plate-like structures with aspect ratios of 1.35 to 1.44 for the top orientation and 4.80 to 9.14 for the side orientation. These values are used to estimate the specific surface areas (SSAs) of the minerals, which are compared to Brunauer-Emmett-Teller (BET) surface area measurements. Through this study, we present a simple method for determining the aspect ratios of aerosolized samples, rather than relying on literature values of model systems. As a result, this technique should provide a better method for determining the optical properties of mineral dust particles.</p><p>Copyright 2014 American Association for Aerosol Research</p></div

Influence of Ions on the Size Dependent Morphology of Aerosol Particles

The study of aerosol particles composed of mixtures of organic and inorganic compounds provides insights for understanding chemistry in the atmosphere as well as information about phase transitions of systems under confinement. In the submicron size regime, we have previously found that liquid–liquid phase separation can be inhibited at sufficiently small particle diameters leading to phase separated particles at larger sizes and homogeneous particles below a threshold diameter. In this paper, we have investigated the influence of cations and anions in the inorganic compound (NH4+, Na+, SO42–, HSO4–, and Cl–) on the phase separation of submicron aerosol particles. Each of five salts were studied with two different organic compounds. Surprisingly, a strong dependence on the identity of the cation is evident in the size dependence of the particle morphology, and no dependence on the anion was found. Sodium containing samples exhibit phase separation in particles below 20 nm in diameter, whereas ammonium containing samples cease to undergo phase separation in particles between 45 and 65 nm in diameter. The separation relative humidity for supermicron droplets also depends on the identity of the cation in the inorganic component if the anion is the same across the salts compared. In addition, the correlation between the separation relative humidity and size dependence was investigated and displays a trend but is not a dominant feature of the data. We explain the results in terms of hard and soft ions, where the harder cation (Na+) leads to phase separation down to smaller sizes while the softer cation (NH4+) prevents phase separation and causes particles up to a larger diameter to remain homogeneous. This study has implications for atmospheric chemistry in regions dominated by sea spray aerosol, which contains sodium as the primary cation, when compared to continental aerosol, where ammonium is an abundant cation. Additionally, these findings can be used to understand the influence of cations on the phase transitions of confined materials

Heterogeneous Ice Nucleation in Model Crystalline Porous Organic Polymers: Influence of Pore Size on Immersion Freezing

Heterogeneous ice nucleation activity is affected by aerosol particle composition, crystallinity, pore size, and surface area. However, these surface properties are not well understood, regarding how they act to promote ice nucleation and growth to form ice clouds. Therefore, synthesized materials for which surface properties can be tuned were examined in immersion freezing mode in this study. To establish the relationship between particle surface properties and efficiency of ice nucleation, materials, here, covalent organic frameworks (COFs), with different pore diameters and degrees of crystallinity (ordering), were characterized. Results showed that out of all the highly crystalline COFs, the sample with a pore diameter between 2 and 3 nm exhibited the most efficient ice nucleation activity. We posit that the highly crystalline structures with ordered pores have an optimal pore diameter where the ice nucleation activity is maximized and that the not highly crystalline structures with nonordered pores have more sites for ice nucleation. The results were compared and discussed in the context of other synthesized porous particle systems. Such studies give insight into how material features impact ice nucleation activity

pH Dependence of Liquid–Liquid Phase Separation in Organic Aerosol

Atmospheric aerosol particles influence climate through their direct and indirect effects. These impacts depend in part on the morphology of the particles, which is determined by their composition. The effect of pH on morphology was investigated using particles composed of 3-methylglutaric acid and ammonium sulfate by manipulating the starting pH of the bulk solution through the addition of aqueous sodium hydroxide. Efflorescence, deliquescence, phase separation, and mixing transitions were observed with optical microscopy. Due to changes in its protonation states, the solubility of the organic component increases with increasing pH, which shifts the location of the separation relative humidity (SRH) from 78.7% for the fully protonated acid to 63.9% for the fully deprotonated acid. Surprisingly, this shift in the SRH leads to hysteresis between the SRH and the mixing relative humidity (MRH). Particle pH has the greatest effect on phase transitions that require nucleus formation, that is, efflorescence and SRH

Size Dependence of Organic/Inorganic Aerosol Morphology and the Role of Oxidation and Aromaticity of the Organic Component

Atmospheric aerosol particles can exist in a phase separated state depending on their chemical components and size as well as relative humidity and temperature conditions, although the effects of these conditions on particle morphology are not well constrained. Whether a system is phase separated has implications for new particle growth, cloud condensation nucleus formation, ice nucleation, and heterogeneous chemistry. In this study, the identity of the organic species in a binary organic-inorganic phase separating system was found to influence the phase separation properties of these internally mixed aerosol particles. Aerosol particles composed of a carboxylic acid, ammonium sulfate, and water were generated, dried, and characterized using transmission electron microscopy, which revealed the influence of aromaticity and the oxidation of the organic component on the size dependence of phase separation. Organic oxidation was defined by the elemental oxygen to carbon ratio (O:C ratio) and lipophilicity (characterized by the negative distribution coefficient at pH 5.5, −log D5.5) for each compound. The span of particle diameters at which both phase-separated and homogeneous particles are found, or the transition region, was evaluated using a logistic regression to calculate the diameters at which there is a 20%, 50%, and 80% probability of a phase separated morphology. The seven systems containing aliphatic organic species showed a positive correlation between the particle diameters in the transition region and organic oxidation, while the four systems containing aromatic organic species showed transition regions with a tentative negative correlation until phase separation was arrested. Overall, these results show how the aromaticity and oxygen content of organic species can determine the morphologies of environmentally relevant aerosol particles and may provide improved constraints for particle-resolved atmospheric models

Cryo-Transmission Electron Microscopy Imaging of the Morphology of Submicrometer Aerosol Containing Organic Acids and Ammonium Sulfate

The effects of aerosol particles on heterogeneous atmospheric chemistry and climate are determined in part by the internal arrangement of compounds within the particles. To characterize the morphology of internally mixed aerosol particles in the accumulation mode size regime, we have used cryo-transmission electron microscopy to investigate the phase separation behavior of dry, submicrometer particles composed of ammonium sulfate mixed with carboxylic acids (adipic, azelaic, citric, glutaric, malonic, pimelic, suberic, and succinic acid). Determining the morphology of dry particles is important for understanding laboratory studies of aerosol optical properties, reactivity, and cloud condensation nucleus activity, results from field instruments where aerosol particles are dried prior to analysis, and atmospheric processes like deposition mode heterogeneous ice nucleation that occur on dried particles. We observe homogeneous morphologies for highly soluble organic compounds. For organic compounds with limited aqueous solubility, partially engulfed structures are observed. At intermediate aqueous solubilities, small particles are homogeneous and larger particles are partially engulfed. Results are compared to previous studies of liquid–liquid phase separation in supermicrometer particles and the impact of these dry particle morphologies on aerosol–climate interactions are discussed

Competitive Adsorption of Acetic Acid and Water on Kaolinite

Mineral dust is prevalent in the atmosphere as a result of emissions from natural and anthropogenic sources. As mineral dust particles undergo long-distance transport, they are exposed to trace gases and water vapor. We have characterized the interactions of acetic acid on kaolinite using diffuse reflectance infrared Fourier transform spectroscopy and molecular modeling to determine the chemisorbed species present. After the addition of acetic acid, gas-phase water was introduced to explore how water vapor competes with acetic acid for surface sites. We found that four chemisorbed acetate species are present on kaolinite after exposure to acetic acid in which acetate bonds through a monodentate, bidenatate, or bidentate bridging linkage with an aluminum atom. These species exhibit varying levels of stability after the introduction of water, indicating that water vapor affects the adsorption of organic acids. These results indicate that the type of chemisorbed species determines its stability toward competitive adsorption, which has potential implications for atmospheric composition and ice nucleation

Size Dependence of the Structure of Organic Aerosol

The effects of aerosol particles on heterogeneous atmospheric chemistry and climate are determined in part by the internal arrangement of compounds within the particles. We have used cryo-transmission electron microscopy to investigate the phase separation behavior of model organic aerosol composed of ammonium sulfate internally mixed with succinic or pimelic acid. We have found that no particle with a diameter <170 nm for succinic acid and 270 nm for pimelic acid is phase separated. Larger particles adopt a phase separated, partially engulfed structure. We therefore demonstrate that phase separation of aerosol particles is dependent on particle size and discuss implications for aerosol–climate interactions