The goal of this thesis is to investigate the kinetics and amount of SO2 uptake on hematite, which will act as a representative of mineral dust aerosol. The environmental reaction chamber used here will allow the variation of water vapor pressure to examine the effect of relative humidity (RH) on these parameters. The role of a common atmospheric oxidant, ozone, in the uptake process will also be investigated. The results will be presented with emphasis on the role of hematite in mineral dust aerosols as a sink of SO2, and the possible acidification of hematite particles through heterogeneous reaction pathways.

It is the future of the stratospheric ozone layer, which protects life at Earth’s surface from harmful ultraviolet (UV) radiation, that is the focus of the present work. Fundamental changes in the composition and structure of the stratosphere in response to anthropogenic climate forcing may lead to catastrophic ozone loss under current, and even reduced, stratospheric halogen loading. In particular, the evolution toward a colder, wetter stratosphere, threatens to enhance the heterogeneous conversion of inorganic halogen from its reservoir species to its catalytically active forms, and thus promote in situ ozone loss. Water vapor concentrations control the availability of reactive surface area, which facilitates heterogeneous chemistry. Furthermore, the rates of the key heterogeneous processes are tightly controlled by the ambient humidity. Thus, credible predictions of UV dosage require a quantitative understanding of both the sensitivity of these chemical mechanisms to water vapor concentrations, and an elucidation of the processes controlling stratospheric water vapor concentrations. Toward this end, we present a set of four case studies utilizing high resolution in situ data acquired aboard NASA aircraft during upper atmospheric research missions over the past two decades. 1) We examine the broad scale humidity structure of the upper troposphere and lower stratosphere from the midlatitudes to the tropics, focusing on cirrus formation and dehydration at the cold-point tropical tropopause. The data show evidence for frequent supersaturation in clear air, and sustained supersaturation in the presence of cirrus. These results challenge the strict thermal control of the tropical tropopause. 2) We investigate the likelihood of cirrus-initiated activation of chlorine in the midlatitude lower stratosphere. At midlatitudes the transition from conditions near saturation below the local tropopause to undersaturated air above greatly reduces the probability of heterogeneous activation and in situ ozone loss in this region. 3) We probe the details of heterogeneous processing in the wintertime Arctic vortex, and find that in situ measurements of OH provide incontrovertible evidence for the heterogeneous reaction of HOCl with HCl. This reaction is critical to sustaining catalytically active chlorine and prolonging ozone loss in the springtime vortex. 4) We revisit the topic of midlatitude ozone loss with an emphasis upon the response of ozone in this region to changes in the chemical composition and thermal structure of the lower stratosphere induced by anthropogenic climate change. Specifically, we show evidence for episodic moisture plumes in the overworld stratosphere generated by the rapid evaporation of ice injected into this region by deep convection, and find that these high water vapor plumes have the potential to alter the humidity of the lower stratosphere, and drastically increase the rate of heterogeneous chemistry and in situ ozone loss, given sufficient reactive surface. / Earth and Planetary Sciences

Mineral dust aerosols emitted from the Earth crust during various natural and anthropogenic processes continuously alter the chemical balance of the atmosphere via heterogeneous processes and thus, impact on the global climate. Understanding of heterogeneous chemistry and photochemistry on mineral dust has become vital to accurately predict the effect of mineral dust loading on the Earth's atmosphere. Here, laboratory measurements are coupled with model studies to understand heterogeneous chemistry and photochemistry in the atmosphere with the specific focus on reactions on mineral oxide surfaces. Heterogeneous uptake of gas phase HNO3 on well characterized metal oxides, oxyhydroxides and carbonates emphasized binding of nitric acid to these surfaces in different modes including monodentate, bidentate and bridging under dry conditions. It is becoming increasingly clear that the heterogeneous chemistry, including uptake of HNO3, is a function of relative humidity (RH) as water on the surface of these particles can enhance or inhibit its reactivity depending on the reaction. All the studied model systems showed a significant uptake of water with the highest uptake by CaCO3. Quantitative analysis of water uptake indicated formation of multilayers of water over these reactive surfaces. Under humid conditions, two water solvated nitrate coordination modes were observed that is inner-sphere and outer-sphere, which differ by nitrate proximity to the surface. Photochemical conversion of nitric acid to gas phase nitrous oxide, nitric oxide and nitrogen dioxide through an adsorbed nitrate intermediate under different atmospherically relevant conditions is shown using transmittance FTIR and XPS analysis. The relative ratio and product yields of these gas phase products change with relative humidity. Photochemistry of adsorbed nitrate on mineral aerosol dust may be influenced by the presence of other distinct gases in the atmosphere making it complicated to understand. This thesis converses formation of active nitrogen, NOx and N2O, and chlorine, ClOx, species in the presence of co-adsorbed trace gases, that could potentially regulate the peak concentration and geographical distribution of atmospheric ozone. Here we report formation of atmospheric N2O, from the photodecomposition of adsorbed nitrate in the presence of co-adsorbed NH3 via an abiotic mechanism that is favorable in the presence of light, relative humidity and a surface. Estimated annual production of N2O over the continental United States is 9.3+0.7/-5.3 Gg N2O, ~5% of total U.S. anthropogenic N2O emissions. Not only NH2 but also gaseous HCl react with adsorbed nitrate to activate "inert" N and Cl reservoir species, yielding NOCl, NOx, Cl and Cl2, through adsorbed nitrate under different atmospherically relevant conditions. Mineral dust aerosol is a major source of bioavailable iron to the ocean with an annual deposition of ~ 450 Tg of dust into the open ocean waters. In this study, we report enhanced Fe dissolution from nano scale Fe-containing minerals, i.e.alpha-FeOOH, beyond the surface area effects that can be attributed to the presence of more reactive sites on specific crystal planes exposed. We further report with clear evidence that aggregation impacts on dissolution. Proton-promoted dissolution of nanorods is nearly or completely quenched in the aggregated state. Acid type, presence of oxyanions and light are several other key factors responsible for regulating for iron dissolution. The work reported in this thesis provides insight into the heterogeneous chemistry and photochemistry of mineral dust aerosol under different atmospherically relevant conditions.