Date of Award

8-2016

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

First Advisor

Paul B. Shepson

Committee Chair

Paul B. Shepson

Committee Member 1

Harshvardhan Harshvardhan

Committee Member 2

Peter T. Kissinger

Committee Member 3

Garth J. Simpson

Abstract

The photochemically-induced destruction of ground-level Arctic ozone in the Arctic occurs at the onset of spring, in concert with polar sunrise. Solar radiation is believed to stimulate a series of reactions that cause the production and release of molecular halogens from frozen, salty surfaces, though this mechanism is not yet well understood. The subsequent photolysis of molecular halogens produces reactive halogen atoms that remove ozone from the atmosphere in these so-called “Ozone Depletion Events” (ODEs). Given that much of the Arctic region is sunlit, meteorologically stable, and covered by saline ice and snow, it is expected that ODEs could be a phenomenon that occurs across the entire Arctic region. Indeed, an ever-growing body of evidence from coastal sites indicates that Arctic air masses devoid of O3 most often pass over sea ice-covered regions before arriving at an observation site, suggesting ODE chemistry occurs upwind over the frozen Arctic Ocean. However, outside of coastal observations, there exist very few long-term observations from the Arctic Ocean from which quantitative assessments of basic ODE characteristics can be made.

This work presents the interpretation of ODEs through unique chemical and meteorological observations from several ice-tethered buoys deployed around the Arctic Ocean. These observations include detection of ozone, bromine monoxide, and measurements of temperature, relative humidity, atmospheric pressure, wind speed, and wind direction. To assess whether the O-Buoys were observing locally based depletion chemistry or the transport of ozone-poor air masses, periods of ozone decay were interpreted based on current understanding of ozone depletion kinetics, which are believed to follow a pseudo-first order rate law. In addition, the spatial extents of ODEs were estimated using air mass trajectory modeling to assess whether they are a localized or synoptic phenomenon. Results indicate that current understanding of the responsible chemical mechanisms are lacking, ODEs are observed primarily due to air mass transport (even in the Arctic Ocean), or some combination of both. Air mass trajectory modeling was also used in tandem with remote sensing observations of sea ice to determine the types of surfaces air masses were exposed to before arriving at O-Buoys. The impact of surface exposure was subsequently compared with local meteorology to assess which variables had the most effect on O 3 variability. For two observation sites, the impact of local meteorology was significantly stronger than air mass history, while a third was inconclusive.

Finally, this work tests the viability of the hypothesis that initial production of molecular halogens from frozen saline surfaces results from photolytic production of the hydroxyl radical, and could be enhanced in the presence of O3. This investigation was enabled by a custom frozen-walled flow reactor coupled with chemical ionization spectrometry. It was found that hydroxyl radical could indeed promote the production and release of iodine, bromine, and chlorine, and that this production could be enhanced in the presence of ozone.

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