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Interactions between societal, natural, and infrastructure systems can be beneficial or harmful to society. Society benefits from natural systems by being provided with the basic necessities of life (air, water, and food). However, events such as stratospheric ozone depletion demonstrate that society ultimately can be harmed by societal impacts on natural systems. Domain knowledge is developed from observation of natural, societal, and infrastructure systems. Domain knowledge is contained within scientific knowledge and engineering knowledge. Scientific knowledge is gained through structured observation and rigorous analysis of natural and societal systems. Engineering knowledge is partially developed from scientific knowledge and is used to manipulate natural and societal systems. Technology is the application of engineering knowledge. In the past two centuries scientific and engineering knowledge have produced technologies that affect the interaction between societal and natural systems. Although scientists and engineers are in positions to advise on policies to address problems involving societal/natural system interactions, their contributions are not always fully utilized. This research examines feedback mechanisms that describe societal, natural, and infrastructure system interaction to develop an improved understanding of the dynamic interactions between society, natural systems, infrastructure systems, scientific and engineering knowledge, technology, and public policy. These interactions are investing through and opposing case study analysis performed using computer simulation modeling. The stratospheric ozone depletion study represents a case in which domain experts successfully influenced public policy. The U.S. civilian nuclear power study represents a case in which domain experts were less successful in influencing public policy. The system dynamics methodology is used to construct these two highly integrated models of societal-natural system interaction. Individual model sectors, based on existing theory, describe natural/infrastructure systems, knowledge and technology development, societal risk perception, and public policy. The work reveals that the influence of scientists and engineers in the public policy is due in part to their ability to shift dominance between causal feedback mechanisms that seek to minimize societal risk from natural systems and feedback mechanisms that seek to minimize the economic risk of increased regulations. The ability to alter feedback mechanism dominance is not solely dependent upon scientists and engineers ability to develop knowledge but to a larger extent depends on their ability to interact with policy makers and society when describing issues involving natural and infrastructure systems.

Understanding the spatiotemporal pattern of near-surface ozone is the key part of polar atmospheric environment. The near-surface ozone can be depleted by the catalytic bromine chemistry in the heterogeneous phase but produced due to the snow photochemistry of nitrogen. In addition to the local chemistry, ozone pattern is also affected by regional meteorology and air-mass transport. Since the polar region is quite sensitive to the climate change, these conditions can be also affected by climate change and variability. Based on the analysis of large amount of dataset combined with in-situ observations, satellite measurements, model simulations, and global reanalysis data, the characteristics of polar ozone pattern and relation to the regional and large-scale atmospheric situations were investigated. At first, the characteristics of tropospheric ozone depletion events (ODEs) in the Arctic spring (April 2008) with satellite measured BrO and backtrajectories. Analysis of these data shows that the ODEs are due to either local halogen chemistry or short-range transport from adjacent high-BrO regions. Sometimes local ozone loss is surprisingly deep, particularly the unstable boundary layer at Churchill seems contribute to free-tropospheric BrO. Continually the influences of large-scale atmospheric patterns to the polar surface ozone are investigated. In years with frequent ODEs at Barrow and Alert, the WP teleconnection pattern is usually in its negative phase, during which the Pacific jet is strengthened but the storm track from western Pacific is weakened. Both factors tend to reduce the transport of ozone-rich airmass from mid-latitudes to the Arctic, creating a favorable environment for the Arctic ODEs. Comparison between Barrow and Alert shows the initiation of ODEs in spring is decided by the solar intensity and the termination is by the surface air temperature. Monthly frequency of ODEs also indicate the wind strength from the Arctic Ocean is largely influential to ODEs. The surface ozone at South Pole reveals year-round reversal trends during 3 decades, which is consistent with what lower-tropospheric temperature shows. Their strong correlation implies the possibility of large meridional mixing in warm conditions, which enhances the background level of ozone and nitrogen at South Pole.

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Charge-induced adsorption is a subject of significance to environmental and biological systems. Ice surface is believed to get charged with potassium deposition. Compared to uncharged ice film, the work function of charged ice film is significantly reduced due to the formation of metastable delocalized excess surface electrons donated by potassium atoms on ice. This charging effect is found to be dependent on temperature. It is also reported that adsorption of carbon tetrachloride would occur drastically on charged ice surface while almost no adsorption was observed on uncharged ice surface at low temperature. In addition, the results strongly agree with the cosmic-ray-driven electron-induced reaction (CRE) model for ozone depletion.

A ground-based, zenith-sky, UV-visible triple grating spectrometer was installed at the Polar Environment Atmospheric Research Laboratory (PEARL) in the Canadian High Arctic during polar springtime from 2004 to 2007 as part of the Canadian Arctic ACE (Atmospheric Chemistry Experiment) Validation Campaigns. From the solar spectra, ozone, NO2, and BrO vertical column densities (VCDs) have been retrieved using the DOAS (Differential Optical Absorption Spectroscopy) technique. This spectrometer, the UT-GBS (University of Toronto Ground-Based Spectrometer), was also deployed as part of the fourth Middle Atmosphere Nitrogen TRend Assessment (MANTRA) campaign in Vanscoy, Saskatchewan in August and September 2004. A near-identical spectrometer, the PEARL-GBS, was permanently installed at PEARL in August 2006 as part of the refurbishment of the laboratory by CANDAC (Canadian Network for the Detection of Atmospheric Change). Since then, the instrument has been making continuous measurements, with the exception of during polar night. Vertical columns of ozone and NO2 can be retrieved year-round. During the 2007 sunrise campaign, differential slant column densities (DSCDs) of OClO and VCDs of BrO were also retrieved. Ozone and NO2 DSCDs and VCDs from the UT-GBS were compared to the DSCDs and VCDs from three other UV-visible, ground-based, grating spectrometers that also participated in the MANTRA and Eureka campaigns. Two methods developed by the UV-visible Working Group of the NDACC (Network for the Detection of Atmospheric Composition Change) were followed. During MANTRA, the instruments were found to partially meet the NDACC standards. The comparisons from Eureka were an improvement on the MANTRA comparisons, and also partially met the NDACC standards. In 2007, the columns from the UT-GBS and PEARL-GBS were compared, and were found to agree within the NDACC standards for both species. Ozone and NO2 VCDs from the ground-based instruments were also compared to integrated partial columns from the ACE-FTS (ACE-Fourier Transform Spectrometer) and ACE-MAESTRO (ACE-Measurements of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation) on board the ACE satellite. ACE-FTS partial columns were found to agree with the ground-based total columns, while the ACE-MAESTRO partial columns were found to be smaller than expected for ozone and larger than expected for NO2.

A ground-based, zenith-sky, UV-visible triple grating spectrometer was installed at the Polar Environment Atmospheric Research Laboratory (PEARL) in the Canadian High Arctic during polar springtime from 2004 to 2007 as part of the Canadian Arctic ACE (Atmospheric Chemistry Experiment) Validation Campaigns. From the solar spectra, ozone, NO2, and BrO vertical column densities (VCDs) have been retrieved using the DOAS (Differential Optical Absorption Spectroscopy) technique. This spectrometer, the UT-GBS (University of Toronto Ground-Based Spectrometer), was also deployed as part of the fourth Middle Atmosphere Nitrogen TRend Assessment (MANTRA) campaign in Vanscoy, Saskatchewan in August and September 2004. A near-identical spectrometer, the PEARL-GBS, was permanently installed at PEARL in August 2006 as part of the refurbishment of the laboratory by CANDAC (Canadian Network for the Detection of Atmospheric Change). Since then, the instrument has been making continuous measurements, with the exception of during polar night. Vertical columns of ozone and NO2 can be retrieved year-round. During the 2007 sunrise campaign, differential slant column densities (DSCDs) of OClO and VCDs of BrO were also retrieved. Ozone and NO2 DSCDs and VCDs from the UT-GBS were compared to the DSCDs and VCDs from three other UV-visible, ground-based, grating spectrometers that also participated in the MANTRA and Eureka campaigns. Two methods developed by the UV-visible Working Group of the NDACC (Network for the Detection of Atmospheric Composition Change) were followed. During MANTRA, the instruments were found to partially meet the NDACC standards. The comparisons from Eureka were an improvement on the MANTRA comparisons, and also partially met the NDACC standards. In 2007, the columns from the UT-GBS and PEARL-GBS were compared, and were found to agree within the NDACC standards for both species. Ozone and NO2 VCDs from the ground-based instruments were also compared to integrated partial columns from the ACE-FTS (ACE-Fourier Transform Spectrometer) and ACE-MAESTRO (ACE-Measurements of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation) on board the ACE satellite. ACE-FTS partial columns were found to agree with the ground-based total columns, while the ACE-MAESTRO partial columns were found to be smaller than expected for ozone and larger than expected for NO2.

Tierra del Fuego, at the southernmost tip of South America, is influenced by ozone depletion. The landscape of southern and western Tierra de! Fuego is dominated by peatlands; they are important locally and in the context of global climate change, because they store large quantities of organic carbon. To determine the influence of solar ultraviolet-B radiation (UV-B) on a Tierra de! Fuego peatland, we selectively filtered solar UV-Bin ten pairs of plots. Polyfluorine filters were used to create the Near-Ambient-UV-B Treatment ( 90% solar UV-B), and polyester filters to create the Reduced-UV-B Treatment ( 17% solar UV-B). These filters were first installed in October 1996, and were maintained, September-March, for six years. Following previous plant growth measurements and samples of selected microorganisms under the two UV-B treatments (1996-1999), this dissertation is an account of the more detailed measurements made during the second three-year period of treatments (1999-2001 ). Seasonal sampling of the plant community, microfungi, microfauna, and biogeochemistry of the water and nutrients held by the Sphagnum capitulum was introduced, in an attempt to better understand ecosystem function. Solar UV-B reduced Sphagnum height growth, but this was compensated by more compressed and densely packed Sphagnum capitula. Emergent vascular plants, Nothofagus, Empetrum, and Tetroncium, were more affected than Sphagnum by nearambient UV-B. Solar UV-B altered the Sphagnum-capitulum microenvironment, resulting in: more dissolved organic carbon and phosphorous, higher electrical conductivity, and greater acidity under near-ambient UV-B. Additionally, the populations of testate amoebae and some species of fungi were consistently increased; however, microfungal diversity and rotifer, nematode, and mite populations decreased under near-ambient UV-B. Generally, Sphagnum minimizes the leaching of nutrients by effectively holding water at the capitulum. Solar UV-B altered Sphagnum-capitulum morphology, increased the volume of water held, and made this water more acidic and richer in nutrients. Based on these results, if current trends in ozone depletion were to persist over several decades, a reduction in vascular plant growth, and changes in the trophic relationships of the microorganismal community of the Sphagnum capitulum, would be predicted. These responses have the potential to affect peatland carbon storage and nutrient cycling in Tierra del Fuego.

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.

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