Type of Document	Dissertation
Author	Zhu, Lei
URN	etd-11172004-142820
Title	Aqueous Phase Reaction Kinetics of Organic Sulfur Compounds of Atmospheric Interest
Degree	Doctor of Philosophy
Department	Earth and Atmospheric Sciences
Advisory Committee	Advisor Name Title Wine, Paul H. Committee Chair Davis, Douglas Committee Member Huey, Greg Committee Member Nenes, Athanasios Committee Member Weber, Rodney Committee Member Whetten, Robert Committee Member
Keywords	aqueous phase kinetics DMS oxidation organic sulfur aqueous radical chemistry MS-to-NSS ratio
Date of Defense	2004-11-08
Availability	unrestricted
Abstract Dimethyl Sulfide (CH3SCH3, DMS) is the most important natural sulfur compound emitted from the ocean and its oxidation in the atmosphere has been proposed to play an important role in climate modification because some products from DMS oxidation become non-volatile and could participate in particle formation and growth processes. Although it has been demonstrated that aqueous phase reactions are potentially important for understanding DMS oxidation, the kinetics database for aqueous phase transformations is rather limited. In this work, a laser flash photolysis (LFP) – long path UV-visible absorption (LPA) technique was employed to investigate the kinetics of the aqueous phase reactions of four organic sulfur compounds produced from DMS oxidation, i.e., dimethylsulfoxide (DMSO), dimethyl-sulfone (DMSO2), methanesulfinate (MSI) and methanesulfonate (MS), with four important aqueous phase radicals, OH, SO4−, Cl and Cl2−. The temperature-dependent kinetics of the OH and SO4− reactions with DMSO, DMSO2 and MS were studied for the first time. OH is found to be the most reactive, while Cl2− is the least reactive toward all the sulfur species studied. The less oxidized DMSO and MSI are found to be more reactive than the more oxidized DMSO2 and MS for each radical. The kinetic data have been employed in a Trajectory Ensemble Model to simulate DMS oxidation in the marine atmosphere as a means of assessing the contribution of aqueous phase reactions to the growth of particulate matter. For the first time, oxidation of organic sulfur compounds by SO4−, Cl and Cl2− are included in the model to simulate DMS chemistry. Our simulations suggest that aqueous phase reactions contribute >97% of MS and ~90% of NSS (Non-Seasalt Sulfate) production, and aqueous phase reactions of the organic sulfur compounds contribute 30% of total particle mass growth. When our kinetic data for the MS + OH reaction were used in the model, it was found that MS + OH could consume ~20% of MS and produce ~8% of NSS, within 3 days under typical marine atmospheric conditions.
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