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Heterogeneous chemistry of atmospheric mineral dust particles and their resulting cloud-nucleation properties
Abstract
Mineral dust particles are a major component of tropospheric aerosol mass and affect regional and global atmospheric chemistry and climate. Dust particles experience heterogeneous reactions with atmospheric gases that alter the gas and particle-phase chemistry. These in turn influence the warm and cold cloud nucleation ability and optical properties of the dust particles. This dissertation investigates the atmospheric chemistry of mineral dust particles and their role in warm cloud nucleation through a combination of synergistic field measurements, laboratory experiments, and theoretical modeling. In-situ measurements made with a single-particle mass spectrometer during the ACE-Asia field campaign in 2001 provide the motivation for this work. The observed mixing state of the individual ambient particles with secondary organic and inorganic components is described in Chapter 2. A large Asian dust storm occurred during the campaign and produced dramatic changes in the aerosol's composition and mixing state. The effect of particle size and mineralogy on the atmospheric processing of individual dust particles is explored in Chapters 3 & 4. Sulfate was found to accumulate preferentially in submicron iron and aluminosilicate-rich dust particles, while nitrate and chloride were enriched in supermicron calcite-rich dust. The mineral dust (and sea salt particles) were also enriched in oxalic acid, the dominant component of water soluble organic carbon. Chapter 5 explores the roles of gas-phase photochemistry and partitioning of the diacids to the alkaline particles in producing this unique behavior. The effect of the dust's mixing state with secondary organic and inorganic components on the dust particles' solubility, hygroscopicity, and thus warm cloud nucleation properties is explored experimentally and theoretically in Chapter 6. Cloud condensation nucleation (CCN) activation curves revealed that while calcium nitrate and calcium chloride particles were very hygroscopic and CCN-active, due to the high solubility of these compounds, calcium sulfate and calcium oxalate were not. Particles composed of these two sparingly soluble compounds had apparent hygroscopicities similar to pure calcium carbonate. This implies that the commonly made assumption that all dust particles become more hygroscopic after atmospheric processing must be revisited. Calcium sulfate and oxalate represent two forms of aged mineral dust particles that remain non-hygroscopic and thus have poor CCN nucleation ability. The particle generation method (dry versus wet) was found to significantly affect the chemistry and hygroscopicity of the aerosolized particles. Finally, in Chapter 7 the timescale for the atmospheric conversion of insoluble calcite particles to soluble, CCN-active calcium nitrate particles was derived from aerosol flow tube experiments. The reaction rate is rapid was used to estimate the conversion of calcite particles to very hygroscopic particles can occur in just a few hours of exposure to tropospheric levels of nitric acid. This process will therefore be controlled by the availability of nitric acid and its precursors, as opposed to the available atmospheric reaction time
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