Thesis (Ph. D.)--University of Washington, 1999. / Vita. Includes bibliographical references (leaves 180-190).

Thesis (Ph. D.)--Earth and Atmospheric Sciences, Georgia Institute of Technology, 2007. / Robert Dickinson, Committee Member ; Athanasios Nenes, Committee Member ; David Tan, Committee Member ; Armistead Russell, Committee Member ; Yuhang Wang, Committee Chair.

No description available.

No description available.

Mesoporous silica materials containing microporous cavities provided by covalently bound ¦Â-cyclodextrin (CD ICS) were synthesized by co-condensation of a ¦Â-CD functionalized triethoxy silane (CD ICL) with tetraethyl orthosilicate (TEOS) by using neutral amine surfactants as structure directing agents (SDA). CD ICL was prepared by reacting ¦Â-CD with 3-isocyanatopropyltriethoxysilane. IR spectroscopy of CD ICL showed complete disappearance of isocyanato group at 2270 cm-1. 1H NMR results indicate an average of four isocyanate linkers covalently attached to random hydroxyl substituents of each molecule of ¦Â-CD. <p> Nine different CD ICS materials were synthesized using dodecylamine, tetradecylamine or hexadecylamine with ¦Â-CD (2, 4, and 6 mol %) with respect to TEOS. The incorporation of ¦Â-CD within the mesoporous framework was supported by IR, Raman, MALDI TOF MS, solid state 13C NMR CP-MAS and TGA results. Small angle X-ray diffraction results showed a peak at 2¦È ¡Ö 2.20, supporting the presence of an ordered silica mesostructure framework. For materials with same CD loading, the surface area and pore volume doubled as the surfactant from dodecylamine to hexadecylamine. However, as the CD loading increased from 2% to 6%, the surface area decreases by a factor of ~ 1.5. <p>MALDI TOF mass spectrometry showed two peaks at m/z 1157 a.m.u. and 1173 a.m.u. for [¦Â-CD + Na]+ and [¦Â-CD + K]+ respectively due to desorption of ¦Â-CD from the walls of the silica matrix. The 13C NMR CP MAS results showed 13C signals in the region ¦Ä=60-110 ppm due to the nuclei of ¦Â-CD. CD ICS materials were found to be effective as a sorbent in both gas and aqueous phases, respectively. The sorption capacity (mmol/g) of p-nitrophenol increased from 61% to 84% with an increase of CD loading from 2% to 6% and as the alkyl chain length of the SDA increases from dodecylamine to hexadecylamine. The adsorption isotherm of CH3Cl in the gas phase and that of p-nitrophenol in the aqueous phase at ambient temperature adopts a multilayer model of adsorption.

Mesoporous silica materials containing microporous cavities provided by covalently bound ¦Â-cyclodextrin (CD ICS) were synthesized by co-condensation of a ¦Â-CD functionalized triethoxy silane (CD ICL) with tetraethyl orthosilicate (TEOS) by using neutral amine surfactants as structure directing agents (SDA). CD ICL was prepared by reacting ¦Â-CD with 3-isocyanatopropyltriethoxysilane. IR spectroscopy of CD ICL showed complete disappearance of isocyanato group at 2270 cm-1. 1H NMR results indicate an average of four isocyanate linkers covalently attached to random hydroxyl substituents of each molecule of ¦Â-CD. <p> Nine different CD ICS materials were synthesized using dodecylamine, tetradecylamine or hexadecylamine with ¦Â-CD (2, 4, and 6 mol %) with respect to TEOS. The incorporation of ¦Â-CD within the mesoporous framework was supported by IR, Raman, MALDI TOF MS, solid state 13C NMR CP-MAS and TGA results. Small angle X-ray diffraction results showed a peak at 2¦È ¡Ö 2.20, supporting the presence of an ordered silica mesostructure framework. For materials with same CD loading, the surface area and pore volume doubled as the surfactant from dodecylamine to hexadecylamine. However, as the CD loading increased from 2% to 6%, the surface area decreases by a factor of ~ 1.5. <p>MALDI TOF mass spectrometry showed two peaks at m/z 1157 a.m.u. and 1173 a.m.u. for [¦Â-CD + Na]+ and [¦Â-CD + K]+ respectively due to desorption of ¦Â-CD from the walls of the silica matrix. The 13C NMR CP MAS results showed 13C signals in the region ¦Ä=60-110 ppm due to the nuclei of ¦Â-CD. CD ICS materials were found to be effective as a sorbent in both gas and aqueous phases, respectively. The sorption capacity (mmol/g) of p-nitrophenol increased from 61% to 84% with an increase of CD loading from 2% to 6% and as the alkyl chain length of the SDA increases from dodecylamine to hexadecylamine. The adsorption isotherm of CH3Cl in the gas phase and that of p-nitrophenol in the aqueous phase at ambient temperature adopts a multilayer model of adsorption.

Thesis (Ph. D.)--University of Washington, 2007. / Vita. Includes bibliographical references (leaves 188-206).

Methyl halides are trace gases with both natural and anthropogenic origins. Once generated, these gases transport chlorine and bromine into the stratosphere, where they play an important role in ozone depleting catalytic cycles. The Florida Everglades is one location where methyl halide emissions have been proposed to be elevated due to high primary production and ionic halogens. This region also provides a unique study environment due to salt water intrusions, which occur during storm or low marsh water level-high tide events. The purpose of this research was twofold. First, quantification of methyl chloride (CH3Cl) and methyl bromide (CH3Br) production from periphyton mats on a temporal scale was needed. Secondly, to determine how varying concentrations of salinity affect CH3Cl and CH3Br production originating from calcareous periphyton mats within the Everglades. Periphyton was exposed to continuous 12 hour dark/light cycles in varying concentrations of salt water (0, 0.1, 1, 5, and 10 parts per thousand). All water samples were analyzed to determine the production rate of CH3Cl and CH3Br in periphyton samples using a gas chromatograph coupled with an electron capture detector (GC-ECD). Periphyton mats were found to be a producer of CH3Cl in all freshwater (0 parts per thousand) trials and sampling times; however, results from CH3Br analysis found production rates that suggest consumption occurred in the majority of the 0 parts per thousand trials. Production rates for CH3Cl ranged from 0.077 to 0.109 g-1hr-1 after 24 hours, 0.027 to 0.073 pM g-1hr-1 after 48 hours, and 0.034 to 0.047 pM g-1hr-1 after 72 hours. Production rates for the CH3Br freshwater experiments ranged from -0.00025 to 0.00185 pM g-1hr-1 after 24 hours, -0.00022 to -0.00078 pM g-1hr-1 after 48 hours, and -0.00042 to -0.00061 pM g-1hr-1 after 72 hours. This research has also shown that increased salinity does have a significant positive effect on the production of CH3Cl and CH3Br from calcareous periphyton mats, which is important in areas that could be prone to salt water intrusions or rising sea levels due to global climate change.

No description available.

Global simulations of atmospheric methyl chloride (CH3Cl) are conducted using the GEOS-Chem model in order to understand better its sources and sinks. Though CH3Cl is one of the most abundant organic chlorine species in the stratosphere, not much is known about its sources and the budget remains unbalanced. In addition to the known sources (1.5 Tg yr-1) from ocean, biomass burning, incineration/industry, salt marshes, and wetlands, a hypothetical aseasonal biogenic source of 2.9 Tg yr-1 is added in order to match needed emissions. Observations from 7 surface sites and 8 aircraft field experiments are used to evaluate the model simulations. The model results with a priori emissions and sinks reproduce CH3Cl observations at northern mid and high latitudes reasonably well. However, the seasonal variation of CH3Cl at southern mid and high latitudes is severely overestimated. Simulated vertical profiles show disagreements in the vicinities of major sources, principally reflecting the uncertainties in the estimated distributions of our added pseudo-biogenic and the biomass burning sources. Inverse modeling is applied to obtain optimal source distributions of CH3Cl on the basis of surface and aircraft observations and model results. We resolve the seasonal dependence of the biogenic and biomass burning sources for each hemisphere. The aircraft in situ measurements are found to provide better constraints on the emission sources than surface measurements. The a posteriori emissions result in better agreement with the observations particularly at southern high latitudes. The a posteriori biogenic and biomass burning source decrease by 13 and 11% to 2500 and 545 Gg yr-1, respectively, while the a posteriori net ocean source increases by about a factor of 2 to 761 Gg yr-1. The decrease in biomass burning emissions is largely due to the reduction in the emissions in seasons other than spring in the northern hemisphere. The inversion results indicate that the biogenic source has a clear winter minimum in both hemispheres, likely reflecting the decrease of biogenic activity during that season.