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The research presented in this thesis is part of the ongoing effort to better understand the role of atmospheric aerosols in the development of clouds. Cloud condensation nuclei (CCN) are the subset of the aerosol population that can activate and grow into cloud droplets under suitable atmospheric conditions. The supersaturation at which a given CCN will activate is dependent on the particle�s size and composition, but the details of the relationship are not completely understood. CCN observations from the CRYSTAL-FACE (Cirrus Regional Study of Tropical Anvils and Cirrus Layers- Florida Area Cirrus Experiment) field campaign are presented in Chapter 2. These measurements are compared to predictions based on measured aerosol size distributions with an assumed chemical composition to determine whether activation theory is sufficient to describe what is observed. The analysis indicates that, in cases like those included in the study, CCN concentrations can be accurately predicted from the size distribution even in the absence of detailed chemical compositional data.

The research presented in this thesis is part of the ongoing effort to better understand the role of atmospheric aerosols in the development of clouds. Cloud condensation nuclei (CCN) are the subset of the aerosol population that can activate and grow into cloud droplets under suitable atmospheric conditions. The supersaturation at which a given CCN will activate is dependent on the particle�s size and composition, but the details of the relationship are not completely understood. CCN observations from the CRYSTAL-FACE (Cirrus Regional Study of Tropical Anvils and Cirrus Layers- Florida Area Cirrus Experiment) field campaign are presented in Chapter 2. These measurements are compared to predictions based on measured aerosol size distributions with an assumed chemical composition to determine whether activation theory is sufficient to describe what is observed. The analysis indicates that, in cases like those included in the study, CCN concentrations can be accurately predicted from the size distribution even in the absence of detailed chemical compositional data.

The general problems of particle motion in the vicinity of a flat, non-deforming fluid interface is studied. The approximate singularity method used by previous workers in this research group has been generalized to consider the motion of a sphere in any linear velocity field compatible with the existence of the undisturbed flat interface, and the motion of slender rod-like particles which undergo an arbitrary translation or rotation in either a quiescent fluid or in a linear flow. The theory yields the hydrodynamic mobility tensors which are necessary to describe Brownian movement near a phase boundary, as well as general trajectory equations for sedimenting particles near a fluid interface with an arbitrary viscosity ratio. These approximate solution results are in good agreement with both exact-solutions where they are available and experimental data for motion of a sphere near a rigid plane wall. Among the most interesting results for motion of slender bodies is the generalization of Jeffery orbit equations for linear simple shear flow.

The general problems of particle motion in the vicinity of a flat, non-deforming fluid interface is studied. The approximate singularity method used by previous workers in this research group has been generalized to consider the motion of a sphere in any linear velocity field compatible with the existence of the undisturbed flat interface, and the motion of slender rod-like particles which undergo an arbitrary translation or rotation in either a quiescent fluid or in a linear flow. The theory yields the hydrodynamic mobility tensors which are necessary to describe Brownian movement near a phase boundary, as well as general trajectory equations for sedimenting particles near a fluid interface with an arbitrary viscosity ratio. These approximate solution results are in good agreement with both exact-solutions where they are available and experimental data for motion of a sphere near a rigid plane wall. Among the most interesting results for motion of slender bodies is the generalization of Jeffery orbit equations for linear simple shear flow.

Assessing the discrepancy between modeled and observed distributions of aerosols is a persistent problem on many scales. Tools for analyzing the evolution of aerosol size distributions using the adjoint method are presented in idealized box model calculations. The ability to recover information about aerosol growth rates and initial size distributions is assessed given a range of simulated observations of evolving systems. While such tools alone could facilitate analysis of chamber measurements, improving estimates of aerosol sources on regional and global scales requires explicit consideration of many additional chemical and physical processes that govern secondary formation of atmospheric aerosols from emissions of gas-phase precursors. The adjoint of the global chemical transport model GEOS-Chem is derived, affording detailed analysis of the relationship between gas-phase aerosol precursor emissions (SOx, NOx, and NH3) and the subsequent distributions of sulfate - ammonium - nitrate aerosol. Assimilation of surface measurements of sulfate and nitrate aerosol is shown to provide valuable constraints on emissions of ammonia. Adjoint sensitivities are used to propose strategies for air quality control, suggesting, for example, that reduction of SOx emissions in the summer and NH3 emissions in the winter would most effectively reduce non-attainment of aerosol air quality standards. The ability of this model to estimate global distributions of carbonaceous aerosol is also addressed. Based on new yield data from environmental chamber studies, mechanisms for incorporating the dependence of secondary organic aerosol (SOA) formation on NOx concentrations are developed for use in global models. When NOx levels are appropriately accounted for, it is demonstrated that sources such as isoprene and aromatics, previously neglected as sources of aerosol in global models, significantly contribute to predicted SOA burdens downwind of polluted areas (owing to benzene and toluene) and in the free troposphere (owing to isoprene).

Assessing the discrepancy between modeled and observed distributions of aerosols is a persistent problem on many scales. Tools for analyzing the evolution of aerosol size distributions using the adjoint method are presented in idealized box model calculations. The ability to recover information about aerosol growth rates and initial size distributions is assessed given a range of simulated observations of evolving systems. While such tools alone could facilitate analysis of chamber measurements, improving estimates of aerosol sources on regional and global scales requires explicit consideration of many additional chemical and physical processes that govern secondary formation of atmospheric aerosols from emissions of gas-phase precursors. The adjoint of the global chemical transport model GEOS-Chem is derived, affording detailed analysis of the relationship between gas-phase aerosol precursor emissions (SOx, NOx, and NH3) and the subsequent distributions of sulfate - ammonium - nitrate aerosol. Assimilation of surface measurements of sulfate and nitrate aerosol is shown to provide valuable constraints on emissions of ammonia. Adjoint sensitivities are used to propose strategies for air quality control, suggesting, for example, that reduction of SOx emissions in the summer and NH3 emissions in the winter would most effectively reduce non-attainment of aerosol air quality standards. The ability of this model to estimate global distributions of carbonaceous aerosol is also addressed. Based on new yield data from environmental chamber studies, mechanisms for incorporating the dependence of secondary organic aerosol (SOA) formation on NOx concentrations are developed for use in global models. When NOx levels are appropriately accounted for, it is demonstrated that sources such as isoprene and aromatics, previously neglected as sources of aerosol in global models, significantly contribute to predicted SOA burdens downwind of polluted areas (owing to benzene and toluene) and in the free troposphere (owing to isoprene).

Organic species are important constituents of tropospheric particulate matter in remote, rural, and urban areas. Such aerosol can be primary (emitted in the particle phase as solids or liquids) or secondary (formed in situ as condensable vapors) in nature. Secondary organic aerosol (SOA) is formed when products resulting from the gas-phase oxidation of a parent organic species partition to the particle phase. This partitioning can occur via condensation onto existing inorganic aerosol (heterogeneous-heteromolecular nucleation), absorption into an existing organic aerosol, dissolution to the aerosol aqueous phase, or homogeneous-heteromolecular nucleation.

SOA yield is defined as the amount of SOA formed per the amount of a parent organic species that is oxidized. This yield depends functionally on stoichiometric and partitioning coefficients for each of the oxidation products formed and the total amount of organic aerosol mass available to act as absorptive media. Appropriate yield parameters are developed for a series of parent organics using smog chamber experiments. The effects of parent organic structure and the oxidizing species on SOA yield are also examined during the smog chamber experiments. Such yield parameters are used to model SOA formation from the oxidation of biogenic organic species on a global and annual scale. Yield parameters can also be used to define a new concept, the incremental aerosol reactivity for parent organic species, which is a convenient way of ranking parent organics in terms of their SOA-forming potentials.

Organic species are important constituents of tropospheric particulate matter in remote, rural, and urban areas. Such aerosol can be primary (emitted in the particle phase as solids or liquids) or secondary (formed in situ as condensable vapors) in nature. Secondary organic aerosol (SOA) is formed when products resulting from the gas-phase oxidation of a parent organic species partition to the particle phase. This partitioning can occur via condensation onto existing inorganic aerosol (heterogeneous-heteromolecular nucleation), absorption into an existing organic aerosol, dissolution to the aerosol aqueous phase, or homogeneous-heteromolecular nucleation.

SOA yield is defined as the amount of SOA formed per the amount of a parent organic species that is oxidized. This yield depends functionally on stoichiometric and partitioning coefficients for each of the oxidation products formed and the total amount of organic aerosol mass available to act as absorptive media. Appropriate yield parameters are developed for a series of parent organics using smog chamber experiments. The effects of parent organic structure and the oxidizing species on SOA yield are also examined during the smog chamber experiments. Such yield parameters are used to model SOA formation from the oxidation of biogenic organic species on a global and annual scale. Yield parameters can also be used to define a new concept, the incremental aerosol reactivity for parent organic species, which is a convenient way of ranking parent organics in terms of their SOA-forming potentials.

Transport properties of novel sulfonated wholly aromatic copolymers and the state-of-the-art poly(perfluorosulfonic acid) copolymer membrane for fuel cells, Nafion, were compared. Species transport (protons, methanol, water) in hydrated membranes was found to correspond with the water-self diffusion coefficient as measured by pulsed field gradient nuclear magnetic resonance (PFG NMR), which was used as a measure of the state of absorbed water in the membrane. Generally, transport properties decreased in the order Nafion > sulfonated poly(arylene ether sulfone) > sulfonated poly(imide). The water diffusion coefficients as measured by PFG NMR decreased in a similar fashion indicating that more tightly bound water existed in the sulfonated poly(arylene ether sulfone) (BPSH) and sulfonated poly(imide) (sPI) copolymers than in Nafion.

Transport properties of novel sulfonated wholly aromatic copolymers and the state-of-the-art poly(perfluorosulfonic acid) copolymer membrane for fuel cells, Nafion, were compared. Species transport (protons, methanol, water) in hydrated membranes was found to correspond with the water-self diffusion coefficient as measured by pulsed field gradient nuclear magnetic resonance (PFG NMR), which was used as a measure of the state of absorbed water in the membrane. Generally, transport properties decreased in the order Nafion > sulfonated poly(arylene ether sulfone) > sulfonated poly(imide). The water diffusion coefficients as measured by PFG NMR decreased in a similar fashion indicating that more tightly bound water existed in the sulfonated poly(arylene ether sulfone) (BPSH) and sulfonated poly(imide) (sPI) copolymers than in Nafion.