Document Type

Dissertation

Date of Degree

Summer 2011

Degree Name

PhD (Doctor of Philosophy)

Degree In

Chemistry

First Advisor

Vicki H. Grassian

Abstract

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.

Keywords

Heterogeneous chemistry, Iron dissolution, Mineral dust, Ozone depletion, Photochemistry, Redox chemistry

Pages

xxiii, 312 pages

Bibliography

Includes bibliographical references (pages 282-312).

Copyright

Copyright 2011 Gayan Randika Sampath Rubasinghege

Included in

Chemistry Commons

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