Aerosols are known to have a large, uncertain effect on air quality and climate. Chemical processing of organic material in aqueous aerosols is known to form secondary organic aerosols (SOA), which make up a significant portion of particulate mass in the atmosphere. However, lack of clarity surrounding the importance of each source of SOA to total aerosol mass contributes to the uncertainties in their environmental impact. Disagreements between chemical models and field measurements suggest that some processes are misrepresented or are missing in current models. This work considers three pathways of SOA formation using Gas-Aerosol Model for Mechanism Analysis (GAMMA), a photochemical box model developed by the McNeill group featuring coupled gas phase and detailed aqueous phase aerosol chemistry. Imidazole-2-carboxaldehyde (IC), a light-absorbing organic species, has been observed to contribute to SOA formation as a photosensitizer. Currently, the extent of photosensitized reactions in ambient aerosols remains poorly constrained. Reactive uptake coefficients were determined from experimental studies of IC-containing aerosols and scaled for ambient simulations in GAMMA. Results of remote ambient simulations show that IC is unlikely to be a significant source of SOA largely due to its lack of abundance in atmospheric aerosols. Humic-like substances (HULIS) have also been experimentally shown to catalyze SOA formation through photosensitizer chemistry. We use GAMMA to quantify the uptake kinetics of limonene in these photosensitizer experiments. Ambient GAMMA simulations of this SOA formation pathway show that limonene-HULIS photosensitizer chemistry can contribute up to 65% of total aqueous SOA at pH 4. Further laboratory studies are recommended for this SOA source to assess the need for its inclusion in aerosol models. Chemical processing of organic material in cloudwater is another known source of SOA. We use GAMMA to consider the impact of the coupled effect of processing in both aqueous aerosol and cloudwater on isoprene epoxydiol (IEPOX) SOA. Simulations show that cloudwater at pH 3 – 4 can also be a potentially significant source of IEPOX SOA, largely due to higher water content in cloudwater than in aerosols. Thus, cloud processing may be a significant contributor to IEPOX SOA formation and could account for differences between predicted SOA mass and ambient measurements where mass transfer limitations in aerosol particles can be expected. This work concludes with recommendations for future work in GAMMA. Parameterization of glyoxal reactive uptake could allow for more accurate predictions of glyoxal oxidation product distributions. The inclusion of online thermodynamic calculations of inorganic species in GAMMA can better constrain several multiphase chemical processes, such as the highly pH-dependent uptake of IEPOX and sulfate formation. Updated detailed mechanisms of transition metal ion chemistry would also improve predictions of sulfate formation.

No description available.

Dust forecasting has become important to military operations over the past three decades. Rules of thumb have been the primary resource for forecasting dust. In recent years, algorithms for weather models have been created to produce atmospheric dust concentration forecasts and are now coming into use operationally. The question becomes how good are the models and what causes errors in their forecasts? This study examines the accuracy of the U. S. Navy's Coupled Ocean Atmospheric Mesoscale Model dust module during the United Arab Emirates Unified Aerosol Experiment. The study also attempts to determine what causes any error if present. The primary method to verify the model's aerial coverage accuracy is through equitable threat score. Case studies are then conducted to verify the scores and identify sources of any errors identified. Results indicate the model performs well with respect to sourcing dust plumes. Errors in modeled aerial coverage as compared to real world observations appear to be the result of an inability for the model to properly advect suspended dust near the surface layer. Unconfirmed dust plumes in the model seemed to be the result of inaccurate surface characteristics.

Thesis (M.S.)--University of Nevada, Reno, 2004. / "December 2004." Includes bibliographical references. Online version available on the World Wide Web.

No description available.

Thesis (M.Sc.)--York University, 2004. Graduate Programme in Chemistry. / Typescript. Includes bibliographical references (leaves 117-120). Also available on the Internet. MODE OF ACCESS via web browser by entering the following URL:http://gateway.proquest.com/openurl?url%5Fver=Z39.88-2004&res%5Fdat=xri:pqdiss&rft%5Fval%5Ffmt=info:ofi/fmt:kev:mtx:dissertation&rft%5Fdat=xri:pqdiss:MQ99407

Thesis (Ph. D.)--University of Washington, 2006. / Vita. Includes bibliographical references (leaves 151-164).

Global warming theories continue to overestimate their predictions of increased mean global temperatures (Hudson 1991). This would imply that some other influence is counteracting the global warming influences; i.e. a cooling effect. Cloud albedo characteristics are currently being researched to determine the impact clouds have on the net cooling of the atmosphere in relation to the global warming theory. These characteristics are influenced by the type, size, composition, and abundance of aerosol particles that act as cloud condensation nuclei. This study employs Tandem Differential Mobility Analyzer (TDMA) data collected in the vicinity of Japan during the Asian Aerosol Characterization Experiment (ACE-Asia) to investigate the influence of aerosol concentration and composition on the light scattering properties of clouds. Measurements of particle size (Dp), particle growth factor (GF), and relative humidity (RH) yield critical supersaturations (Sc) with the assumption that the soluble part of the particle is composed primarily of one substance. This indirect composition analysis allows us to determine whether the aerosol was internally mixed (particles have uniform composition and yield a single-peak distribution or similar growth factors) or externally mixed (different particles have different compositions yielding multiple peaks in the distribution). Through the use of calculated supersaturations, we can gain insight into cloud droplet activation properties of the samples for various aerosol types, which ultimately allows us to look at the influence of these particles on albedo characteristics of clouds formed by these particles.

The freezing of model atmospheric aerosols – specifically, model cirrus cloud particles – was investigated through laboratory studies of supercooled water aerosols. Water droplets with radii of 1 – 2.7 µm were exposed to well-defined temperature profiles ranging from 240 – 230 K in a cryogenic flow tube apparatus, and observed using infrared extinction spectroscopy. A computational characterization procedure, based on theories of light scattering, was used to determine the size and phase composition of aerosols from extinction spectra. The procedure showed large ice fractions at uncharacteristically warm temperatures, which was attributed to the formation of ordered, “ice-like” clusters of molecules in supercooled water. Temperature-dependent complex indices of refraction were determined from the supercooled water extinction spectra, and showed changes reflecting this ordered formation. Taking the “ice-like” character of clusters into account, the homogeneous nucleation point for micrometre-sized water aerosols was determined to be 236.2 K. A microphysical model was developed to determine temperature-dependent, volume- and surface-based homogeneous nucleation rates from experimental freezing data. The model results indicated that surface nucleation was the dominant process for our range of experimental conditions. This was supported by separate studies of smaller, 0.63 and 0.75 µm radius aerosols, with larger surface-to-volume ratios. An optical microscopy apparatus was placed in the cryogenic flow tube to allow real-time imaging of particles in freezing experiments. The imaging studies demonstrated the utility of the microscopy apparatus for the observation and classification of ice crystal habits. Ray tracing and image processing algorithms were used to analyze particle geometry and size. The latter was used to validate the size retrievals from the aerosol characterization procedure. Additional studies probed the changes in the optical properties of crystalline ammonium sulfate, (NH₄)₂SO₄, due to the paraelectric-to-ferroelectric transition at 223 K. Temperature- dependent refractive indices were determined from crystalline (NH₄)₂SO₄ extinction spectra. Only small changes in these values were observed down to 223 K, below which significant changes were observed, due to the changes in lattice structure accompanying the ferroelectric transition.

The freezing of model atmospheric aerosols – specifically, model cirrus cloud particles – was investigated through laboratory studies of supercooled water aerosols. Water droplets with radii of 1 – 2.7 µm were exposed to well-defined temperature profiles ranging from 240 – 230 K in a cryogenic flow tube apparatus, and observed using infrared extinction spectroscopy. A computational characterization procedure, based on theories of light scattering, was used to determine the size and phase composition of aerosols from extinction spectra. The procedure showed large ice fractions at uncharacteristically warm temperatures, which was attributed to the formation of ordered, “ice-like” clusters of molecules in supercooled water. Temperature-dependent complex indices of refraction were determined from the supercooled water extinction spectra, and showed changes reflecting this ordered formation. Taking the “ice-like” character of clusters into account, the homogeneous nucleation point for micrometre-sized water aerosols was determined to be 236.2 K. A microphysical model was developed to determine temperature-dependent, volume- and surface-based homogeneous nucleation rates from experimental freezing data. The model results indicated that surface nucleation was the dominant process for our range of experimental conditions. This was supported by separate studies of smaller, 0.63 and 0.75 µm radius aerosols, with larger surface-to-volume ratios. An optical microscopy apparatus was placed in the cryogenic flow tube to allow real-time imaging of particles in freezing experiments. The imaging studies demonstrated the utility of the microscopy apparatus for the observation and classification of ice crystal habits. Ray tracing and image processing algorithms were used to analyze particle geometry and size. The latter was used to validate the size retrievals from the aerosol characterization procedure. Additional studies probed the changes in the optical properties of crystalline ammonium sulfate, (NH₄)₂SO₄, due to the paraelectric-to-ferroelectric transition at 223 K. Temperature- dependent refractive indices were determined from crystalline (NH₄)₂SO₄ extinction spectra. Only small changes in these values were observed down to 223 K, below which significant changes were observed, due to the changes in lattice structure accompanying the ferroelectric transition.