Nitrogen (N) is known to be a limiting factor in peatlands and as such, the vegetation present has adapted to living in low N conditions. This makes such ecosystems particularly vulnerable to increases in the deposition of reactive N (Nr), which may result in significant changes to its biodiversity and biogeochemistry. Since the industrial revolution, the amount of anthropogenic Nr globally has increased from ~15 Tg N y-1 in the 1860’s to ~187 Tg N y-1 in 2005, and is estimated to reach ~267 Tg N yr-1 by 2050 (Galloway et al. 2004, Galloway et al. 2008). Consequences include acidification, loss of biodiversity, changes in vegetation, N-saturation, eutrophication, health impacts and the release of greenhouse gases.Objectives of this thesis were (i) to measure key components of the N-budget at Auchencorth Moss, a Scottish moorland, for a two year period (Jan 2009 – Dec 2010) and (ii) to compare current deposition rates with those measured 14/15 years previously. Annual fluxes of N inputs were estimated from measurements of wet only deposition, estimates of N-fixation deposition and from atmospheric deposition modelled from hourly concentrations of N containing gases and aerosols. Exports were estimated from stream measurements and from atmospheric emissions modelled from hourly concentrations. Organic N is often an underreported part of the N-cycle, but the results presented here suggest it is an important part of the N story. An attempt to identify (dissolved organic nitrogen) DON compounds in both precipitation and stream water was made using GC×GC-NCD. Ten unique compounds were detected, of which only five could be identified: pyrrole, benzonitrile, dodecylamine, N-nitrosodipropylamine and decylamine. Pyrrole, benzonitrile and three unknown compounds were present in both precipitation and stream samples. Ammonia (NH3) fluxes were measured over a 7 month period in 2009 using a wet-chemistry gradient system with online analysis and calculated with the aerodynamic gradient method. The results were used to refine a bi-directional dynamic exchange model. Several parameters were updated, including an increased stomatal emission potential from 180 to 350, a reduction of the minimum cuticular resistance (Rw,min) used to calculate Rw from 20 s m-1 to 15 s m-1 and an increase in the leaching rate (Kr¬) from the leaf surfaces from -0.01 to -0.1 s-1. The exchange parameterisations used to estimate HNO3, HONO and the aerosol compounds were taken from the literature and earlier studies at the site.Overall, Auchencorth was found to accumulate N, with deposition exceeding export by -1.61 kg N ha-1 yr-1. The main N deposition was from NH3, followed by wet deposition of ammonium. DON, which is not routinely included in N budgets, contributed 6.5% of total deposition. The largest loss of N was as DON via the stream with N losses of -5.31 kg N ha-1 yr-1 or 71.8% of total export. Between 1995 and 2009/2010, deposition decreased by 0.81 kg N ha-1 yr-1, with the wet deposition of inorganic nitrogen decreasing by 25.2%, but dry deposition increasing by 12.5%. DON, N2O and N-fixation were not included in the comparison as they were not measured in 1995.This thesis has demonstrated that DON is an important parameter in the overall N budget, and should be routinely measured when assessing the N status of ecosystems.

Atmospheric mercury deposition, known to be a major source of mercury to aquatic and terrestrial environments, was studied at an urban site in Orlando, FL. Precipitation sampling was conducted from September 2003 to May 2006 at a Mercury Deposition Network site located on the University of Central Florida campus. Weekly rainfall and mercury wet deposition data were gathered from this site, which provided the framework of data for this study. Historical mercury wet deposition data from several sites in Florida were used to develop a regression model to predict mercury deposition at any location in Florida. Stormwater runoff from a 2-acre impervious surface at this study area was monitored during the spring and summer of 2005. Runoff water quality was analyzed to characterize mercury dry deposition. Atmospheric monitoring was also conducted during this period to study the interaction of atmospheric constituents on wet and dry deposition patterns. Spatial and seasonal trends for the entire state suggest 80% of Florida's rainfall and mercury deposition occur during the wet season. A strong linear correlation was established between rainfall depth and mercury deposition (R2 = 0.8). Prediction equations for the entire state, for both wet and dry seasons, were strongly correlated with measured data. The results of two unique methods to quantify dry deposition were similar at this site during this study period. Runoff monitored at this site contained significant levels of mercury, primarily in particulate form (58%). The vast majority of particulate mercury was flushed from the surface during storm events, while significant dissolved fractions remained. Runoff mercury concentrations were consistently higher than rainfall mercury, suggesting dry deposition accounted for 22% of total mercury in runoff. Atmospheric monitoring at this location showed gaseous elemental mercury was the dominant form (99.5%) followed by reactive gaseous mercury (0.3%) and particulate mercury (0.2%). Comparison of the contributions of wet and dry deposition suggested 80% of total mercury deposition was wet deposited during this study, while dry deposition accounted for the remaining 20%. Statistical correlations revealed rainfall scavenging of reactive gaseous mercury was the main factor controlling dry deposition.

According to the United Nations, 55% of the world's population currently lives in urban areas and which is projected to increase to 67% by 2050. Thus, it is imperative that effective strategies are developed to mitigate urban pollution. Complementing field experiments, computational fluid dynamics (CFD) analyses are becoming an effective strategy for identifying critical factors that influence urban pollution and its mitigation. This thesis focuses on two scales of the urban micro-climate environment: (i) evaluation of LES simulations with a simplified grid for modeling pollution dispersion in a street canyon and (ii) investigation of the effects of leaf surface micro-characteristics, wind speed, and particle sizes on the dry deposition of fine particulate matter (PM2.5). The first of these studies focuses on reproducing the pollution dispersion in a street canyon measured in a wind tunnel at Karlsruhe Institute of Technology (KIT), Germany. A simplified grid with the Large Eddy Simulations (LES) approach for canyon ratio W/H = 1 is proposed with the goal to reduce the computational cost by eliminating the need to model the entire canyon while striving to preserve the mixing induced by individual jets used to model vehicle emission in the experiment. LES is also capable of providing transient flow field and pollution concentration data not available with widely-used steady approaches such as RANS. The time-dependent information is crucial for pollution mitigation since pedestrians are usually exposed to pollution on a short-time basis. The predictions are in satisfactory agreement with the experiment for W/H = 1, yielding the Pearson correlation coefficient R = 0.81, with better performance near the leeward wall. Due to the small span modeled, three-dimensional instabilities fail to develop which could probably explain the overprediction of pollution concentration near ground level. However, other LES investigations where the full canyon was modeled also observed over-predictions. The use of a discrete emission source was not observed to provide benefits. The current model could be further improved by using a larger spanwise domain with a continuous line source to allow large wavelength instabilities to develop and increase turbulent diffusion. The second part of this thesis investigates the impact of trichome morphology and wind speed on the deposition of 0.3 μm and 1.0 μm particles on leaves. Using the one-way coupling approach to predict the fluid-particle interactions with the assumption that all particles that impact the leaf or trichome surface deposit, trichomes of 5 μm and 20 μm in diameter are modeled as equally spaced and uniform cylinders on an infinitely large plane. The results show that trichome diameter, density, and wind speed have a favorable impact on deposition velocity. Comparing to the smooth leaf, the presence of the thicker 20 μm hairs increases the deposition velocity by 1.5 – 4 times, whereas, the presence of short 5um trichomes reduces the deposition by 15 - 45%. Increasing trichome height from H/D = 20 to 30 shows benefits for the thinner trichomes but lowers the deposition for the densely packed thicker trichomes. Less aerosol deposition is also observed when the particle diameter increases from 0.3 μm to 1.0 μm. Due to the non-uniform contributions of these various traits, a non-dimensional ratio Rhp is proposed to model the aerosol deposition on leaf surface at wind speed of 1 m/s which yields a satisfactory linear correlation coefficient of 0.89 for 0 < R_hp < 0.3. Comparing to other published field and wind tunnel experiments conducted on a much larger scale, the deposition velocities predicted are at the lower end (U_dep^* = 0.002 to 0.012 cm/s) because of the idealized conditions. Nonetheless, the results still offer valuable insight into the effects of trichome morphology on pollutant deposition in isolation from other macro-factors. / Master of Science / According to the United Nations, 55% of the world’s population currently lives in urban areas and which is projected to increase to 67% by 2050. Thus, it is imperative that effective strategies are developed to mitigate urban pollution. Complementing field experiments, computational fluid dynamics (CFD) analyses are becoming an effective strategy for identifying critical factors that influence urban pollution and its mitigation. This thesis focuses on two scales of the urban micro-climate environment: (i) evaluation of Large Eddy Simulation (LES) with a simplified method for modeling pollution dispersion in a street canyon and (ii) investigation of the effects of leaf surface micro-characteristics, wind speed, and particle sizes on the dry deposition of fine particulate matter (PM2.5). The first of these studies focuses on reproducing the pollution dispersion in a street canyon measured in a wind tunnel at Karlsruhe Institute of Technology (KIT), Germany. A simplified grid with the LES approach for canyon ratio W/H = 1 is proposed. The goal of this study is to reduce the computational cost by modelling the canyon with a very thin span instead of the entire canyon while providing time-dependent information which is crucial for pollution mitigation since pedestrians are usually exposed to pollution on a short-time basis. The predictions are in satisfactory agreement with the experiment for W/H = 1 with better performance near the leeward wall (i.e. the left wall) and overprediction of pollution concentration near ground level – as observed by other LES investigations. The current model could be further improved by using a larger spanwise domain with a continuous line source to allow instabilities to develop, thus improve prediction accuracy. The second part of this thesis investigates the impact of trichome (i.e. a hair or an outgrowth from leaf surface) morphology and wind speed on the deposition of 0.3 mm and 1.0 mm particles on leaves. The results show that trichome diameter, density, and wind speed have a favorable impact on deposition velocity. Less aerosol deposition is also observed when the particle diameter increases from 0.3 mm to 1.0 mm. No clear effects is observed by altering the trichome height. Due to the non-uniform contributions of these various traits, a non-dimensional ratio D∗ �D∗ �2 Rhp = hair hair is proposed to model the aerosol deposition on leaf surface at wind speed of D∗ H∗ S∗ p hair hair 1 m/s which yields a satisfactory linear correlation coefficient of 0.89 for 0 < Rhp < 0.3. This ratio includes trichome diameter (D∗ ), height (H∗ ), spacing (S∗ ) as well as the ratio of hair hair hair trichome diameter to particle diameter (D∗ /D∗ ). The results offer valuable insight into the hair p effects of trichome morphology on pollutant deposition in isolation from other macro-factors.

The terrestrial ecosystem is an integral component of the Earth System. Constant atmosphere-biosphere exchanges of energy and material affect both the physics and chemistry of the atmosphere. While the general roles of terrestrial ecosystems in regulating ozone and particulate matter air pollution have long been acknowledged, our understanding at both individual process and system level are far from perfect. Also, new process-level discoveries about terrestrial atmosphere-biosphere exchanges are not timely incorporated in numerical models routinely used to study and forecast air quality. These hinder our ability to understand how air quality respond to environmental changes and variabilities. Chapter 1 of this dissertation provides a brief overview on these topics. In Chapter 2 of this dissertation (Wong et al., 2019), we conduct global long-term simulations of ozone dry deposition velocity with four different types of dry deposition parameterizations. We find that none of the tested parameterizations universally stands out in terms of matching observed ozone deposition velocity over different land cover types. Combining this with sensitivity simulations from a global 3-D atmospheric chemistry model (GEOS-Chem), we find that the choice of dry deposition parameterizations can affect the mean, trend and variability of simulated surface O3 level. In Chapter 3 of this dissertation (Wong et al., 2022), we analyze long-term ozone flux observation from three field sites to examine the effects of extreme heat and dryness on ozone deposition. We find that non-stomatal ozone uptake tends to increase during hot days, which either partially offsets or dominates over the reduction in stomatal ozone uptake anticipated by ecophysiological theory. While the response of ozone deposition to dryness is more varied, changes in non-stomatal deposition are usually important. Current dry deposition parameterizations often fail to capture such changes in non-stomatal ozone uptake, resulting in considerable potential error in simulated surface ozone level during hot and dry days. In Chapter 4 of this dissertation (Wong and Geddes, 2021), we conduct global GEOS-Chem numerical experiments with anthropogenic emission inventories and land surface remote sensing products to compare the effects land cover versus land management changes on O3 and fine particulate matter air quality over 1992 – 2014. We find that land cover has stronger effects on O3, while land management has stronger effects on fine particulate matter pollution. We also find that land management has significantly altered regional and global nitrogen deposition, and therefore the risk of critical load exceedance. Chapter 5 of this dissertation includes the concluding remarks and suggestions for future work. In addition, I outline and present the preliminary result from a project examining the future of soil reactive nitrogen emissions and their impacts on air quality.

<p dir="ltr">The origins and deposition of nitrate in dust traps in Mojave Desert are examined in this thesis. Two main hypotheses are tested: (1) most of the dust in the traps comes from local soil, implying that the nitrate content is primarily derived from the soil; and (2) wet deposition is the primary source of nitrate found in the environments, implying that precipitation processes play an important role in nitrate accumulation. To test these hypotheses, we collected data from 11 dust trap from locations in of the US Geological Survey's long-term investigation of dust composition and influx rates. Dust and soil samples were analyzed for ions to determine their origins and the contributions of local vs distant sources. Our findings show that the fraction of soil-derived nitrate (<i>f</i>_soilNO₃^-) is consistently low at all traps, hardly reaching 0.03, whereas the atmospheric nitrate percentage (<i>f</i>_atmNO₃^-) is usually close to or equal to 1. This shows that atmospheric sources play a substantial role in the nitrate levels detected in dust traps. Nitrate contributions are also significantly influenced by sedimentary and geological settings, such as the distinctions between alluvium and playa regions. Playas, which are composed of silt and clay, may have higher nitrate concentrations than alluvial plains, indicating that external dust inputs are significant. The second hypothesis's results show that nitrate deposition in the study area is primarily from dry sources, with dry deposition values ranging from 0.68 to 10.84 NO₃⁻/kg/ha/yr, averaging 4.12 NO₃⁻/kg/ha/yr, and wet deposition values averaging 1.09 NO₃⁻/kg/ha/yr. This observation challenges the hypothesis that wet deposition is the primary source of nitrate. The dominance of dry deposition is further supported by low amounts of precipitation and a weak correlation between precipitation and dust deposition. This study concludes that although local soil has a role in nitrate levels in dust traps in the study site, it is not the primary source, external sources and dry deposition account for the majority of nitrate in the dustpan</p>

In Canada, more than 35 million kilograms of pesticide active ingredients are applied annually on agricultural land with about 84% of this mass applied in the Canadian Prairies Provinces. Pesticide residues may become airborne through post-volatilization losses from land, water or vegetative surfaces, via wind-eroded soil, and by spray drift during pesticide application. Once in the air, pesticides may be dispersed and transported as parent molecules or as degradation products. Currently used and legacy pesticide air concentrations were measured in the agricultural region of the Prairie Provinces and the northern subarctic and arctic regions of Canada in 2005 and 2007. More intensive air sampling was conducted across the province of Manitoba in 2008 and 2009. Separate wet versus dry atmospheric deposition samples and wetland water samples were also taken in these years. In general, pesticides were detected in the monitored environmental media as mixtures with the frequency and concentrations detected being largest for pesticides that were applied on-site. Although the most commonly used herbicides in western Canadian agriculture were frequently present in the air in the regions where they are applied, they appeared infrequently and at low levels in the Canadian Subarctic, Arctic, and remote sites far from agricultural pesticide applications. Results also indicated that the concentrations of legacy pesticides such as lindane (γ-HCH) and its manufacturing by-product prior to 1971 (α-HCH) continued to decrease over time in the Canadian environment. Air concentrations of pesticides in agricultural regions, and subsequent wet and dry atmospheric deposition, contaminated surface water following periods of pesticide application. Dry deposition contributed 12–51% of the total deposition. Calculations were performed to predict wetland water column pesticide concentrations based on total atmospheric deposits alone. The estimated concentrations were closest to actual concentrations for MCPA and predictions were also reasonable for a range of other herbicides, but a source other than atmospheric deposition was clearly relevant to the detection of clopyralid in the wetland water-column. Individual herbicide concentrations did not exceed Canadian water quality guidelines for the protection of aquatic life.

Aerodynamically rough surfaces of forests provide for efficient air/ canopy exchange of mass, heat and momentum. In that context, the effects of forest edges come into focus, and therefore, coastal-zone forests constitute aparticular concern. Aerosol-sink modelling is of importance to the global-scalecontext, because sink strengths influence the concentration of aerosol particles in the atmosphere, and that concentration, in turn, influences climate. Dry deposition models are insufficient due to a lack of semi-empirical data and because of difficulties in parameterization of the efficiency (E) with which leaves capture aerosols. Quantifications of such parameters promote possibilities for modelling aerosol-sink processes within various canopy layers. This thesis focuses on studies of sea-salt aerosol dry deposition within models of oak canopies exposed to artificially generated aerosols in a wind tunnel. The overall goal is to advance the understanding of deposition processes in forest ecosystems. Aims are to determine capture efficiencies and deposition velocities (Vd) for oak (Quercus robur L.), to investigate E and Vd dependence on aerosol particle size, wind velocity and vegetation structural elements such as Leaf Area Index (LAI), to explore edge effects on deposition, to relate my results to natural situations in the field, and to address modelling applications. This thesis is a result of five studies. The first study is based on developing awind tunnel approach with a main focus on establishing reference conditions.The next step is to quantify E and provide estimates of how E, with respect toa well defined mass-vs-particle-size distribution, varies with wind speed. To that end, a special wash-off technique is developed. Finally, edge effects ondeposition processes are investigated. Results demonstrate that forest ecosystems would experience substantially increased deposition at edges. The findings suggest that field measurements of deposition in the interior of a forest “island” in an otherwise open landscape would underestimate the deposition to the entire forest. Results clearly indicate needs for further research on the effects of LAI on capture efficiency and deposition velocity. The obtained capture efficiencies can be translated into deposition velocities for trees with a specific leaf area. An increase of Vd with increasing wind speed is found, and is consistent with other studies. Results confirm advantages of the wind tunnel approach, including its ability to enable experiments under controlled conditions. However, several problems require that explicit sub-models be developed of wind-speed dependent effects on leaf posture in the aerosol flow field and that gradients in relative humidity close to leaf surfaces need further attention. The results also propose needs for a range of further experimental investigations regarding aerosol deposition across the complete sea-to-land aerodynamic transition.

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Actuellement, le dépôt sec d’aérosols en milieu urbain est peu connu du fait d’un manque de données.Ces connaissances sont pourtant indispensables pour comprendre les flux de polluants dans les villes et estimer l’exposition d’habitants à des rayonnements ionisants dans le cas d’aérosols radioactifs. Un apport de données permettrait en outre d’améliorer la modélisation du dépôt dans ce milieu. Une approche expérimentale originale est employée pour étudier le dépôt sec d’aérosols submicroniques sur des surfaces urbaines. L’association d’expérimentations en soufflerie et in situ et l’utilisation de traceurs permettent de mesurer des vitesses de dépôt sec et d’étudier les différents phénomènes physiques qui régissent ce dépôt en milieu urbain. Ces données sont associées à des conditions de météorologie et de turbulence quantifiées par des mesures. Cet ensemble permet de hiérarchiser l’influence des principaux phénomènes physiques pour chaque type d’expérimentation. Notamment,des phénomènes différents doivent être considérés prépondérants dans le cas d’expositions chroniques ou aigües des surfaces urbaines aux particules atmosphériques. / Aerosol dry deposition is not much known for urban areas due to the lack of data. Knowledge on this phenomenon is necessary to understand pollutant fluxes in cities and to estimate inhabitant exposition to ionizing radiation of radioactive aerosols. A data providing could enable to enhance dry deposition models for these areas. An original experimental approach is performed to study submicron aerosol dry deposition on urban surfaces. Wind tunnel coupled to in situ experiments give results to study different physical phenomen on governing dry deposition. Dry deposition velocities are measured using aerosol tracers. These data are associated to turbulent and meteorological measured conditions. This database permits to classify the principal physical phenomenon for each experiment type. Finally, different phenomenon must be considered for chronic and acute exposition of urban surfaces to atmospheric particles.