Ozone depletion

Summary

Ozone depletion consists of two related events observed since the late 1970s: a steady lowering of about four percent in the total amount of ozone in Earth's atmosphere, and a much larger springtime decrease in stratospheric ozone (the ozone layer) around Earth's polar regions. The latter phenomenon is referred to as the ozone hole. There are also springtime polar tropospheric ozone depletion events in addition to these stratospheric events. The main causes of ozone depletion and the ozone hole are manufactured chemicals, especially manufactured halocarbon refrigerants, solvents, propellants, and foam-blowing agents (chlorofluorocarbons (CFCs), HCFCs, halons), referred to as ozone-depleting substances (ODS). These compounds are transported into the stratosphere by turbulent mixing after being emitted from the surface, mixing much faster than the molecules can settle. Once in the stratosphere, they release atoms from the halogen group through photodissociation, whic

Official source

https://en.wikipedia.org/wiki/Ozone_depletion

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Emissions of ozone precursors have been regulated in Europe since around 1990 with air quality control measures, which resulted in reductions of nitrogen oxides and volatile organic compounds concentrations. In order to understand how these measures have affected tropospheric ozone, it is important to investigate its long-term temporal evolution in different types of environments and various geographic regions. Uncertainties in ozone long-term trends are associated to variations originating from meteorological influence on ozone. Also, ozone temporal evolution can vary significantly among different regions and types of environment. In this PhD thesis we used sophisticated statistical tools, and developed robust statistical approaches to study long-term trends of tropospheric ozone that reflect emissions reductions. First, we focus on a meteorological adjustment of ozone observations in order to derive long-term trends with lower uncertainties compared to common practices. In addition, a classification scheme for stations in Europe is needed to interpret response of ozone in site groups with similar spatio-temporal characteristics. A detailed long-term trend analysis was performed based on decomposition of the mean ozone observations in the time domain. The different time-dependent variations of ozone were extracted, namely the long-term trend, seasonal and short-term variability. This allows subtraction of the meteorologically driven seasonal variation from the observations and estimation of long-term trends on de-seasonalized concentrations. In addition, ozone peak concentrations were investigated using a localized regression approach, which corrects for meteorological influence. The meteorological adjustment of the mean and peak ozone allows estimation of long-term trends with lower uncertainty. A site grouping in Europe was developed using the long-term and seasonal variations of ozone. The implemented clustering approach based on the long-term variation resulted in a site type classification while a geographical classification was achieved on the seasonal variation. We observed that, despite the implementation of regulations, mean ozone has been increasing in most of the sites until mid-2000s, although, afterwards, a decline or a leveling off was observed. The point when the trend changes from increasing to decreasing depends on the site type; the closer a site locates to emission sources the later the change occurred. Also, it was concluded that with time urban and rural environments become more similar in terms of ozone concentrations. On the other hand, peak ozone has been reducing in most stations, while in sites close to emissions it increased until mid-2000s when it started to level off. The influence of air pollutants hemispheric transport is depicted in remote sites, where ozone increased until beginning of 2000s and decreased afterwards. A two-dimensional classification scheme, reflecting site type and region, has showed that mainly the site type influences ozone long-term trends, while the location is more important for temporal changes in ozone inter-annual cycle and relationship to temperature.

EPFL2020

During the last century, urban pollution has increased with the growth of cities. Urban air quality has become a high priority as it is directly linked to concerns such as human exposure and health. The present work is dedicated to urban air quality modeling with focus on urban meteorology. The main goal is to improve meteorological and air quality simulations in urban areas. Based on measurements and numerical air quality simulations, Chapter 3 describes the meteorological situation and tests an emission inventory for an ozone pollution episode in Mexico City (2 March 1997), in order to determine the principal factors to be accounted in an air quality study. The Mexico City case shows the great influence of meteorological conditions and pollutant emissions on air quality. A thorough understanding of the phenomena governing the meteorological conditions, like small scale convergence, and an accurate emission inventory validated by VOC measurements in the city, are sensitive elements in an air quality study. In Chapter 4, the presence of an Urban Heat Island (UHI) is underlined over the city of Basel (Switzerland) with the BUBBLE measurements. Further on, the ability of aLMo (the operational weather prediction model of MeteoSwiss) to reproduce the effect of a city on the boundary layer atmospheric flow fields is investigated. Results show that aLMo is not able to reproduce the UHI and hence that its surface scheme based on the Monin-Obukhov Similarity Theory (MOST) is not adapted for the urban areas. Therefore, the Buildings Effects Parametrization (BEP) which has been developed by Martilli et al.(2002) especially for urban areas, is implemented in aLMo. Results show that alMo is now able to reproduce the main behavior of the urban boundary layer as the UHI and BEP has hence a real enhancement potential for aLMo. Chapter 5 shows the sensitivity of aLMo with respect to its vertical resolution. In order to limit the sensitivity of aLMo to the grid resolution, BEP is modified. The mesoscale model furnishes the upper boundary conditions for the inner calculation of BEP. That is, BEP recalculates independently the vertical profiles of wind, temperature and energy based on the surface fluxes of momentum, heat and turbulent kinetic energy. The results obtained show a decrease in the sensitivity to the resolution and a better agreement with the measurements. Furthermore, the modified version of BEP gives additional meteorological fields (temperature, wind and TKE) in the urban canopy. The computed temperature in the urban canopy shows a good agreement with measurements in a Basel street canyon. This work shows that it is not necessary to have a high resolution for taking into account modification of the atmospheric flow fields induced by a city.

EPFL2007

Gamma titanium aluminide (γ-TiAl) based alloys are very interesting materials for structural applications at elevated temperatures owing to the combination of high specific strength, good oxidation, creep and fatigue resistance. However, their relatively poor ductility and fracture toughness remain important obstacles for their industrial applications in engineering components. The mechanical properties of these alloys, namely the poor room temperature ductility, as well as the yield stress, creep and fracture resistance, can be significantly improved by controlling the microstructure. These alloys undergo solid state phase transformations upon cooling from the high temperature α phase, which results in formation of different types of microstructures depending on the cooling conditions and the alloy composition. Low and moderate cooling rates lead to the precipitation of the γ phase as parallel plates within the α matrix, followed by the α → α2 ordering reaction. As a result of this transformation, the characteristic lamellar structure of TiAl is produced. Rapid cooling leads to a massive transformation from α to γ. It has been shown that the massive microstructure can be used as a precursor to obtain a refined microstructure through a subsequent tempering in the α + γ phase field. However, obtaining a fully massive microstructure at all depths in a component can be difficult to achieve. Numerical simulation of microstructure formation can be used as a tool to anticipate the microstructure distribution in a component depending on the local chemistry and cooling conditions. The main objective of this work was to develop microstructure models describing the formation of the massive and lamellar microstructures. Two distinct modeling approaches have been used. The first approach is a deterministic model having for objective to predict the microstructure distribution in a cast and heat treated component. The model was designed to be integrated into a FEM or FDM heat flow solver in order to calculate microstructural quantities such as the proportion of phases and lamellar spacings at each nodal point of the mesh. The modeling approach is based on a combination of nucleation and growth laws which take into account the specific mechanisms of each phase transformation. Nucleation of massive and lamellar γ is described with classical nucleation theory, accounting for the fact that nuclei are formed predominantly at α/α grain boundaries. Growth of the massive γ grains is based on theory for interface-controlled reactions. A modified Zener model is used to calculate the thickening rate of the lamellar γ precipitates. The model incorporates the effect of particle impingement and coverage of the nucleation sites by the growing phases. The driving pressures of the phase transformations are obtained from Thermo-Calc based on the actual temperature and matrix composition. The deterministic approach was used to calculate CCT diagrams and lamellar spacings, which showed to be in good agreement with experimental data obtained from dedicated heat treatment experiments and from the literature. The model permitted investigating the influence of cooling rate, alloy chemistry and average α grain size upon the amount of massive γ and the average thickness and spacing of the lamellae. In particular, it indicated that the Al depletion of the α phase during lamellar precipitation seems to play an important role in the suppression of the massive transformation at moderate cooling rate and in the large lamellar spacings observed at low cooling rate. It was also found that Nb additions enhance the formation of massive γ by lowering the lamellar transformation temperature, increasing the T0 temperature and slowing down the lamellar growth due to the low diffusivity of Nb. The second approach was a cellular automaton (CA) model, which was used to describe the formation of the lamellar microstructure on the scale of a few microns. The objective of this approach was to make a direct description of the growth of a precipitate by an interfacial ledge mechanism, and then to evaluate whether the simplifications made in the deterministic model regarding this mechanism are appropriate. The modelling approach is based on the resolution of the diffusion equations in the α and γ phases. The ledge structure at the α/γ interface is described by introducing different types of cells in the CA grid. The CA model was used to describe the formation of the lamellar microstructure at isothermal conditions and at various cooling rates. The thickening kinetics of the lamellae, the lamellar spacings and the overall kinetics of the transformation were calculated with this approach and were compared with the results obtained with the deterministic model. It was found first that the thickening kinetics of the lamellae calculated with the deterministic model are slower than those calculated with the CA model. It was established that the method used in the deterministic model to account for the growth by a ledge mechanism always leads to a growth exponent of 0.5, which is characteristic of diffusion controlled reactions. In contrast, the CA approach yields growth exponents that are comprised between 0.5 and 1, as it is expected for growth in a mixed diffusion/interface controlled mode. The incorporation of a kinetic undercooling term into the deterministic model was found to be an appropriate correction. A good agreement was finally obtained in terms of lamellar spacings and overall kinetics. The underestimated thickening kinetics of the deterministic model was observed to be partly compensated by a higher nucleation rate at the beginning of the transformation. The overall kinetics of the lamellar transformation calculated with the deterministic model was found to be sufficiently accurate to correctly predict the competition between the lamellar and massive microstructures.

EPFL2009

EPFL2007

EPFL2020

EPFL2009