Author ORCID Identifier
Year of Publication
Doctor of Philosophy (PhD)
Arts and Sciences
Dr. Marcelo I. Guzman
Atmospheric aerosols play an important role in climate by scattering and absorbing radiation and by serving as cloud condensation nuclei. An aerosol’s optical or nucleation properties are driven by its chemical composition. Chemical aging of aerosols by atmospheric oxidants, such as ozone, alters the physiochemical properties of aerosol to become more hygroscopic, light absorbing, and viscous during transport. However the mechanism of these transformations is poorly understood. While ozone is a protective and beneficial atmospheric gas in the stratosphere, it is a potent greenhouse gas in the troposphere that traps heat near the Earth’s surface. It also impacts human heath by irritating the respiratory tract and exacerbating cardiovascular diseases. Additionally, ozone can alter the ecosystem through oxidizing plant foliage which can lead to deforestation and crop losses as well. Both gases and aerosols in the troposphere can react with ozone directly and indirectly with hydroxyl radicals. While daytime aging is thought to be primarily driven by photochemical processes and hydroxyl radicals, ozone is thought to be a key player in nighttime or dark aging processes that can alter the physicochemical properties of aerosols. Measured concentrations of trace gases and aged aerosol components in the field are higher than values predicted based on laboratory studies and computer simulations. Consequently, new experimental approaches are needed to narrow the gaps between observations and mechanistic understandings.
In this dissertation, a plume of microdroplets was generated by pneumatically assisted aerosolization and then exposed to a flow of ozone before entering a mass spectrometer. This surface-specific technique allowed for the real-time analysis of reaction products and intermediates at the air-water interface. This work explores the in situ oxidation of iodide, a component of sea spray aerosols, by 0.05 – 13.00 ppmv ozone to explore how heterogeneous oxidation could enhance the production of reactive iodide species. Methods to study the reaction channels and intermediates were also established to not only determine a mechanism of iodide oxidation by ozone, but to enable the study of more complex systems. The developed approach was then applied to examine the oxidation of catechol and its substituted cousins, a family of compounds selected to model biomass burning and combustion emissions, at the air-water interface. While literature suggested that the primary mechanism of catechol oxidation by ozone would be the cleavage of the C1-C2 bond, it was determined that this was only a minor pathway. An indirect oxidation channel dominated heterogeneous processes at the air-water interface, giving rise to hydroxyl and semiquinone radicals that recombine to produce polyhydroxylated aromatics and quinones. This new mechanism of aging represents an overlooked channel by which brown, light-absorbing carbon aerosols are produced in the atmosphere.
In addition, the work investigates how reactions on solid particulate aerosols proceed under variable relative humidity. Thin films were developed alongside a novel flow-through reactor to study of how aerosols are transformed by ozone and hydroxyl radicals when exposed to 50 ppbv - 800 ppmv of ozone. This system was employed to probe how catechol reacts with ozone under variable relative humidity. Further work was undertaken to model the adsorption process at the air-solid interface under variable humidity, permitting the estimation of the reactive uptake of ozone by the film at concentrations (50-200 ppbv) seen in rural and urban areas. Together, these results provide an increased understanding of how heterogeneous oxidation of aerosols contributes to aerosol aging processes as well as free radical production in the troposphere.
Digital Object Identifier (DOI)
Pillar-Little, Elizabeth A., "MECHANISMS OF HETEROGENEOUS OXIDATIONS AT MODEL AEROSOL INTERFACES BY OZONE AND HYDROXYL RADICALS" (2017). Theses and Dissertations--Chemistry. 80.