Downslope flows and regions of enhanced cooling have important impacts on society and the environment. Parameterisation of these often subgrid-scale phenomena in numerical models requires a sound understanding of the underlying physical processes, which has been the overarching aim of this work. A numerical model has been used to characterise the development of a region of enhanced cooling in an idealised alpine valley with width and depth of order 10 and 1 km, respectively, under stable, decoupled, poorly-drained conditions. A focus of this work has been to remove the uncertainty surrounding the forcing mechanisms behind the development of regions of enhanced cooling. The average valley-atmosphere cooling has been found to be almost equally partitioned between radiative and dynamics effects. Complex interactions between the downslope flows and the region of enhanced cooling have been quantified for the first time. For example, relatively large variations in the downslope flows are generally restricted to the region of enhanced cooling and cannot solely be attributed to the analytical model of [McNider, 1982a]. These flow variations generally coincide with return flows above the downslope flows, where a thin region of unstable air occurs, as well as coinciding with elongated downslope flow structures. The impact of these interactions on the dispersion of passive pollutants has been investigated. For example, pollutants are generally trapped within the region of enhanced cooling. The concentration of pollutants within the region of enhanced cooling, emitted over the lower half of the slopes, increase as the emission source moves away from the ground-based inversion that expands from the bottom of the valley. The concentration of pollutants within the region of enhanced cooling is very similar when varying the location of the emission source over the top half of the valley slopes. This work includes a test of the effects of varying the horizontal numerical grid resolution on average valley-atmosphere temperature changes.

Aerosols are thought to have a large effect on the climate, especially through their interactions with clouds. The magnitude and in some cases the sign of aerosol effects on cloud and precipitation are highly uncertain. Part of the uncertainty comes from the multiple competing effects that aerosols have been proposed to have on cloud properties. In addition, covariation of clouds and aerosol properties with changing meteorological conditions has the ability to generate spurious correlations between cloud and aerosol properties. This work presents a new way to investigate aerosol-cloud-precipitation interactions while accounting for the influence of meteorology on cloud and aerosol. The clouds are separated into cloud regimes, which have similar retrieved cloud properties, to investigate the regime dependence of aerosol-cloud-precipitation interactions. The strong aerosol optical depth (AOD)- cloud fraction (CF) correlation is shown to have the ability to generate spurious correlations. The AOD-CF correlation is accounted for by investigating the frequency of transitions between cloud regimes in different aerosol environments. This time-dependent analysis is also extended to investigate the development of precipitation from each of the regimes as a function of their aerosol environment. A modification of the regime transition frequencies consistent with an increase in stratocumulus persistence over ocean is found with increasing AI (aerosol index). Increases in transitions into the deep convective regime and in the precipitation rate consistent with an aerosol invigoration effect are also found over land. Comparisons to model output suggest that a large fraction of the observed effect on the stratocumulus persistence may be due to aerosol indirect effects. The model is not able to reproduce the observed effects on convective cloud, most likely due to the lack of parametrised effects of aerosol on convection. The magnitude of these effects is considerably smaller than correlations found by previous studies, emphasising the importance of meteorological covariation on observed aerosol-cloud-precipitation interactions.

Research during the last two decades has established that variability of the winter polar stratospheric vortex can significantly influence the troposphere, affecting the likelihood of extreme weather events and the skill of long-range weather forecasts. This influence is particularly strong following the rapid breakdown of the vortex in events known as sudden stratospheric warmings (SSWs). This thesis addresses some outstanding issues in our understanding of the dynamics of this stratospheric variability and its influence on the troposphere. First, a geometrical method is developed to characterise two-dimensional polar vortex variability. This method is also able to identify types of SSW in which the vortex is displaced from the pole and those in which it is split in two; known as displaced and split vortex events. It shown to capture vortex variability at least as well as previous methods, but has the advantage of being easily applicable to climate model simulations. This method is subsequently applied to 13 stratosphere-resolving climate models. Almost all models show split vortex events as barotropic and displaced vortex events as baroclinic; a difference also seen in observational reanalysis data. This supports the idea that split vortex events are caused by a resonant excitation of the barotropic mode. Models show consistent differences in the surface response to split and displaced vortex events which do not project stongly onto the annular mode. However, these differences are approximately co-located with lower stratospheric anomalies, suggesting that a local adjustment to stratospheric potential vorticity anomalies is the mechanism behind the different surface responses. Finally, the predictability of the polar stratosphere and its influence on the troposphere is assessed in a stratosphere-resolving seasonal forecast system. Little skill is found in the prediction of the strength of the Northern Hemisphere vortex at lead times beyond one month. However, much greater skill is found for the Southern Hemisphere vortex during austral spring. This allows for forecasts of interannual changes in ozone depletion to be inferred at lead times much beyond previous forecasts. It is further demonstrated that this stratospheric skill descends with time and leads to an enhanced surface skill at lead times of more than three months.

The ice giants, Uranus and Neptune, are the two outermost planets in our solar system. With only one satellite flyby each in the late 1980’s, the ice giants are arguably the least understood of the planets orbiting the Sun. A better understanding of these planets’ atmospheres will not only help satisfy the natural scientific curiosity we have about these distant spheres of gas, but also might provide insight into the dynamics and meteorology of our own planet’s atmosphere. Two new ground-based, near-infrared datasets of the ice giants are studied. Both datasets provide data in a portion of the electromagnetic spectrum that provides good constraint on the size of small scattering particles in the atmospheres’ clouds and haze layers. The broad extent of both telescopes’ spectral coverage allows characterisation of these small particles for a wide range of wavelengths. Both datasets also provide coverage of the 825 nm collision-induced hydrogen-absorption feature, allowing us to disentangle the latitudinal variation of CH4 abundance from the height and vertical extent of clouds in the upper troposphere. A two-cloud model is successfully fitted to IRTF SpeX Uranus data, parameterising both clouds with base altitude, fractional scale height, and total opacity. An optically thick, vertically thin cloud with a base pressure of 1.6 bar, tallest in the midlatitudes, shows strong preference for scattering particles of 1.35 μm radii. Above this cloud lies an optically thin, vertically extended haze extending upward from 1.0 bar and consistent with particles of 0.10 μm radii. An equatorial enrichment of methane abundance and a lower cloud of constant vertical thickness was shown to exist using two independent methods of analysis. Data from Palomar SWIFT of three different latitude regions.

Les composés organiques volatils d’origine biogénique (COVB) contribuent à plus de 90% des émissions des COV dans l'atmosphère. Ces composés sont éliminés de l’atmosphère par réaction avec les photo-oxydants (OH, NO3, Cl et O3) et par photolyse. Ces processus sont gouvernés par un mécanisme en chaîne dont les porteurs sont des radicaux libres tels que les radicaux peroxyles RO2 qui jouent un rôle clé dans la dégradation atmosphérique des COV. Dans ce contexte, cette thèse se concentre d’une part sur l’étude cinétique en température et mécanistique de la réaction d’ozonolyse, la détermination des spectres UV et la photolyse de six COV oxygénés insaturés (trans-2-pentènal, trans-2-hexènal, 2-méthyl-2-pentènal, 1-pentèn-3-ol, cis- 2-pentèn-1-ol et trans-3-hexèn-1-ol), et d’autre part l’étude de la réactivité de trois radicaux peroxyles (CH3OCH2O2, CH3C(O)CH2O2 et (CH3)2C(OH)CH2O2) vis-à-vis des radicaux nitrates à différentes températures. Trois dispositifs expérimentaux sont utilisés : une chambre de simulation atmosphérique couplée à une spectroscopie infrarouge à transformée de Fourier (FTIR) et à une chromatographie en phase gazeuse associée à une spectrométrie de masse (GC/MS), un dispositif de mesure des spectres UV-Visible et la photolyse laser couplée à une spectrométrie UV-visible et diode laser. Ces dispositifs associés à des méthodes de traitement permettent d'extraire des données cinétiques en température, mécanistiques et spectroscopiques. Les paramètres cinétiques obtenus sont utilisés pour estimer les durées de vie atmosphériques des espèces étudiées. Les résultats mécanistiques sont utilisés pour élaborer les mécanismes d’ozonolyse de ces composés. Toutes ces données permettent d’enrichir les bases de données cinétiques, mécanistiques et spectroscopiques qui alimentent les modèles atmosphériques. / Biogenic volatile organic compounds (BVOC) account for 90% of VOC emissions in the atmosphere. These VOCs can be removed from the atmosphere by reaction with photo-oxidants (OH, NO3, Cl and O3) as well as by photolysis. All these processes are governed by a chain mechanism whose carriers are mainly free radicals such as peroxy radicals RO2. Hence the importance of characterizing the reactivity of these species that play a key role in the atmospheric degradation of VOCs. In this context, this thesis focuses on the determination of the temperature dependent kinetic data as well as the mechanism of the ozonolysis reaction and the UV absorption spectra along the photolysis of six unsaturated oxygenated VOCs (trans- 2-pentenal, trans-2-hexenal, 2-methyl-2-pentenal, 1-penten-3-ol, cis-2-penten-1-ol and trans-3-hexen-1-ol). Likewise, the temperature dependent kinetic parameters of the reaction of three peroxy radicals (CH3OCH2O2, CH3C(O)CH2O2 et (CH3)2C(OH)CH2O2) with nitrate radicals were also determined. Three experimental setups coupled to treatment methods were used to extract these data: an atmospheric simulation chamber coupled to both a Fourier-transform infrared spectroscopy (FTIR) and a gas chromatography connected to a mass spectrometry (GC/MS), a device for measuring UV-Visible spectra and a laser photolysis coupled with UV-visible spectrometry and laser diode spectroscopy. The kinetic parameters were used to estimate the atmospheric lifetimes of the studied species. While the mechanistic data were used to establish their ozonolysis mechanisms. All the collected data enrich kinetic, mechanistic and spectroscopic databases, improving atmospheric models specially those involving VOCs.

Gravity waves play a fundamental role in driving the large-scale circulation of the atmosphere. They are influenced both by the variation in their sources and the filtering effects of the winds they encounter as they ascend through the atmosphere. In this thesis we present new evidence that gravity waves play a key role in coupling the troposphere, stratosphere and mesosphere. In particular, we examine the connection of gravity waves to two important large-scale oscillations that occur in the atmosphere, namely the Madden-Julian Oscillation (MJO) in the troposphere and the Mesospheric Semi-Annual Oscillation (MSAO). We present the first ever demonstration that the MJO acts to modulate the global field of gravity waves ascending into the tropical stratosphere. We discover a significant correlation with the MJO zonal-wind anomalies and so suggest that the MJO modulates the stratospheric gravity-wave field through a critical-level wave-filtering mechanism. Strong evidence for this mechanism is provided by consideration of the winds encountered by ascending waves. The Ascension Island meteor radar is used for the first time to measure momentum fluxes over the Island. These measurements are then used to investigate the role of gravity-wave in driving a dramatic and anomalous wind event that was observed to occur during the first westward phase of the MSAO in 2002. Gravity waves are shown to play an important role in driving this event, but the observations presented here also suggest that the current theory of the mechanism describing these anomalous mesospheric wind events is not valid. Both of these studies highlight the critical importance of gravity waves to the dynamics of the atmosphere and highlight the need for further work to truly understand these waves, their processes and their variability.

A new model for the simulation of street canyon atmospheric chemical processing has been developed, by integrating an existing Large-Eddy Simulation (LES) dynamical model of canyon atmospheric motion with a detailed chemical reaction mechanism, the Reduced Chemical Scheme (RCS), comprising 51 chemical species and 136 reactions, based upon a subset of the Master Chemical Mechanism (MCM). The combined LES-RCS model is used to investigate both the effects of mixing and chemical processing upon air quality within an idealised street canyon. The effect of the combination of dynamical (segregation) and chemical effects is determined by comparing the outputs of the full LES-RCS canyon model with those obtained when representing the canyon as a zero-dimensional box model (i.e. assuming mixing is complete and instantaneous). The LES-RCS approach predicts lower (canyon-averaged) levels of NOX, OH and HO2, but higher levels of O3, compared with the box model run under identical chemical and emission conditions. Chemical processing of emissions within the canyon leads to a significant increase in the Ox flux from the canyon into the overlying boundary layer, relative to primary emissions, for the idealised case and a number of pollution scenarios considered. These results demonstrate that within-canyon atmospheric chemical processing can substantially alter the concentrations of pollutants injected into the urban canopy layer, compared with the raw emission rates within the street canyon and that such variations have a considerable effect on average within canyon concentrations and the flux of pollutants out of the canyon into the urban background environment.

This study aims to investigate the physical properties of particles and their implications for source apportionment and health human exposure studies. A wide range of particle number size distribution (PNSD) measurements was conducted in selected environments using state-of-the-art high time resolution instruments. It is found that PNSD varied in different environments, depending on emission sources and atmospheric processes. A mass balance model was used to predict the penetration, infiltration factors, deposition and loss rates of indoor particles. The loss rates of indoor particles, which are mainly subject to deposition, coagulation and evaporation, were found to be a function of particle size and time. Moreover, HTDMA measurements were performed to study the hygroscopic properties of particles in outdoor and indoor environments, and from five major indoor sources. The particles emitted from indoor sources were mostly hydrophobic. An enhanced lung deposition model based on the ICRP and MPPD models was developed to predict the deposition fraction of particles in the human respiratory tract, with consideration of their hygroscopicity. Furthermore, a combination of lung deposition models and the PMF technique was applied to identify which sources are mostly responsible for deposited particles in the different regions of lung.

A high-resolution multi-proxy reconstruction of the Arabian Sea Summer Monsoon (ASSM) intensity over the past 90,000 years has been determined using two marine sediment cores: one from the Somali margin and one from the Indian margin. This reconstruction indicates that changes in monsoon- induced upwelling, primary productivity and denitrification have varied in synchrony with Dansgaard-Oeschger (D-O) cycles. Increased monsoon intensity correlates with warm climate events (interstadials) and decreased monsoon intensity, which coincides with stadials and Heinrich Events, is confirmed by elevated dust concentrations in the marine cores. A comparison of the Somali and Indian margin cores with previously reported studies from the Northern and Western Basin allows the identification of discrete sediment signals from the Indus River, the Arabian Peninsula and from local riverine runoff. Sedimentary deposition on the Indian margin during interglacials is dominated by local terrestrial runoff, whereas during glacial periods increased dust input from the Arabian Peninsula is evident. Both signals are related to changes in the intensity of the ASSM. Monsoon intensity has decreased during the Holocene as the Intertropical Convergence Zone (ITCZ) has moved to a more southerly position. The ASSM-ITCZ relationship (increased ASSM intensity and a northern ITCZ, decreased ASSM intensity and a southern ITCZ) has remained consistent over the last glacial cycle suggesting that global millennial scale climatic variability is in part driven by modulations in tropical hydrological cycle. This ASSM reconstruction provides evidence that rearrangements in the tropical convection system affected atmospheric dust concentrations as well as the concentration and location of atmospheric water vapour. In addition to modulating terrestrial and marine emissions of greenhouse gases, variation in the tropical hydrological cycle provides a mechanism of amplifying and perpetuating millennial-scale climatic changes.

Bibliography: leaves 117-126 / vii, 126 leaves : ill ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Applied Mathematics, 1993