Modeling the single-scattering properties of nonspherical particles in the atmo¬sphere (in particular, ice crystals and dust aerosols) has important applications to climate and remote sensing studies. The first part of the dissertation (Chapters II¬V) reports a combination of exact numerical methods, including the finite-difference time-domain (FDTD), the discrete-dipole-approximation (DDA), and the T-matrix methods, and an approximate method-the physical-geometric optics hybrid (PGOH) method-in the computation of the optical properties of the non-spherical particles in a complete range of size parameters. The major advancements are made on the modeling capabilities of the PGOH method, and the knowledge of the electromag¬netic tunneling effect – a semi-classical scattering effect. This research is important to obtain reliable optical properties of nonspherical particles in a complete range of size parameters with satisfactory accuracy and computational efficiency. The second part (Chapters VI-VII) of the dissertation is to investigate the de¬pendence of the optical properties of ice crystals and mineral dust aerosols in the atmosphere on the spectrum, the particle size and the morphology based on compu¬tational models. Ice crystals in the atmosphere can be classified to be simple regular faceted particles (such as hexagon columns, plates, etc.) and imperfect ice crystals. Modeling of the scattering by regular ice crystals is straightforward, as their morphologies can be easily defined. For imperfect ice crystals, the morphology is quite diverse, which complicates the modeling process. We present an effective approach of using irregular faceted particle to characterize the imperfectness of ice crystals. As an example of application, less-than-unity backscattering color ratio of cirrus clouds is demonstrated and explained theoretically, which provides guidance in the calibra¬tion algorithm for 1.064-µm channel on the Calipso lidar. Dust aerosols have no particular morphology. To develop an approach to modeling the optical properties of realistic dust particles, the principle of using simple shapes (triaxial ellipsoids and nonsymmetric hexahedra) to represent irregular dust particles is explored. Simulated results have been compared with those measured in laboratory for several realistic aerosol samples. Agreement between simulated results and measurement suggests the potential applicability of the two aforementioned aerosol models. We also show the potential impact of the present study to passive and active atmospheric remote sensing and future research works.

Heterogeneous reactions between mineral dust aerosols and gas phase volatile organic compounds have the potential to impact important atmospheric chemical processes. However, little is known about the uptake and reactivity of volatile organic compounds on particulates found in the environment. A Knudsen cell was designed and constructed for providing precise measurement of reaction probabilities within these systems. The instrument was validated through a series of experiments. After validating the Knudsen cell against several key benchmarks, the instrument was used to measure the uptake coefficient for ethanol on particulate silicon dioxide. The uptake coefficient of ethanol on silicon dioxide, a common compound in mineral dust aerosols, was determined to be 7 x 10-7. Therefore, uptake of ethanol on silicon dioxide would be competitive with the loss of other volatile organic compounds on silicon dioxide, which show similar rates of uptake. The Knudsen cell was validated and measured the uptake of ethanol on silicon dioxide, and future work with the Knudsen cell will study the uptake of chemical warfare agent simulants on metal oxides. / Master of Science

Mineral dust aerosols play an important role in atmospheric chemistry through photolysis and heterogeneous uptake. Both mechanisms strongly depend on the size and composition of mineral dust. Because of the complex nature of dust, chemistry modeling commonly relies on simplified assumptions about the properties of dust particles relevant to physiochemical processes. The goal of this thesis is to investigate the impact of size-resolved composition of dust aerosols on atmospheric photochemistry. The relative importance of dust characteristics in photolysis and heterogeneous loss and the relative roles of the two mechanisms on atmospheric photochemistry are investigated. A new block of spectral aerosol optical properties was developed and incorporated into the tropospheric ultraviolet and visible radiation transfer code in order to calculate spectral actinic fluxes and photolysis rates, J-values. The Fuchs-Sutugin approximation was employed to compute mass transfer from gas to dust mineral species and heterogeneous loss rate, kloss,j. The J-values and kloss,j were incorporated into a one-dimensional photochemistry model to simulate the diurnal cycle of a vertical profile of photochemical species. Several cases of dust loading were considered in the clean and polluted marine environments. A size-resolved mineralogical composition was constructed by selecting a range of the mass fraction of the three main mineral species such as iron oxide-containing clay minerals, carbonate-containing species, and quartz. This work demonstrates that differences in microphysical and chemical properties of mineral dust lead to the important changes in spectral optical properties, J-values, and kloss,j. It also shows that non-linear relationships of photochemical species with two mechanisms result in various changes in the photochemical oxidant fields and that the most important factor controlling the photochemistry field is the dust size distribution, followed by the amount of mineral species with high uptake coefficients and the amount of iron oxide-clay aggregates. This work demonstrates that accounting for regional differences in microphysical and chemical properties of mineral dust will improve the assessment of the impact of mineral dust on tropospheric photochemistry. In addition, it suggests that the size and composition of mineral dust will lead to a deeper understanding of the impact of mineral dust on the global climate system.