Ein Teilziel des Projektes KLAPS ist eine auf die Projektregion ausgerichtete Analyse der Ozonbelastung in Abhängigkeit klimatischer Einflussfaktoren. Im vorliegenden Bericht werden die zeitlichen Verläufe der Vorläufersubstanzen und der Einfluss meteorologischer Bedingungen auf die Ozonkonzentration im 21. Jahrhundert untersucht. Die Ergebnisse verweisen auf einen möglichen Anstieg der Ozonkonzentration in den Sommermonaten der nächsten Jahrzehnte allein durch die Auswirkungen des Klimawandels. Entscheidend für die zukünftige Höhe der Ozonkonzentration ist allerdings die Entwicklung der Emissionen im Projektgebiet.

Il a été démontré que l'ozone troposphérique mesuré à la Réunion subit à la fois l'influence des feux de biomasse d'Afrique du Sud et de Madagascar, mais aussi l'influence d'intrusions stratosphériques. Situé à 21° Sud, le site est fortement influencée par le courant jet subtropical en hiver austral mais aussi au printemps austral. Le début des mesures d'ozone troposphérique à la Réunion date de 1992 avec les premiers radiosondages. L'installation d'un lidar dial a permis d'enrichir les mesures d'ozone troposphérique à partir de 1998. Des mesures d'ozone par radiosondages ont également lieu à Irene en Afrique du Sud depuis 1990. En 1998, les sites d'Irene et de la Réunion ont intégré le réseau SHADOZ (Thompson et al. , 2003). Les travaux présentés visent à analyser la base de données ozone de la Réunion avec une approche lagrangienne afin de déterminer l'influence relative des sources photochimique et stratosphérique sur l'ozone troposphérique. Ce travail commence par une étude comparative de la climatologie et des tendances de l'ozone troposphérique pour deux sites de la région : l'île de la Réunion et Irene en Afrique du Sud. Les tendances de l'ozone troposphérique ont été calculées sur l'ensemble de la base de données de la Réunion et d'Irene à la fois sur la colonne troposphérique totale et aussi en subdivisant la troposphère en couches atmosphériques représentatives de la basse, moyenne et haute troposphère. Ce travail d'examen des données, de bilan climatologique et de calcul de tendances a permis de mettre en évidence les caractéristiques spécifiques des données, les caractéristiques climatologiques de l'ozone troposphérique dans la région et de poser une hypothèse sur l'évolution des sources d'ozone dans la région. Par la suite, l'analyse de la base de données ozone de la Réunion à l'aide de l'outil trajectographique lagrangien Lacytraj a permis de mettre en évidence la saisonnalité des intrusions stratosphériques ainsi que leurs caractéristiques saisonnières à savoir la profondeur des intrusions, le rapport de mélange en ozone associé aux masses d'air d'origine stratosphérique, les distributions verticales saisonnières des intrusions stratosphériques.

The ozone formation reaction O+O2+M→O3+M is a unique example of a chemical reaction that leads to an anomalous isotopic composition of the products, most likely due to symmetry - breaking effects. So far, results on other chemical systems that might show similar effects are spurious, even though such claims concerning reactions other than the formation of ozone have been made repeatedly.This applies in particular to the spin forbidden O+CO+M→CO2+M reaction, where two studies report a mass-independent fractionation of about 8%. Nevertheless, the presence of ozone in these experiments raises questions as to the validity of this assertion. We thus make a new attempt to study the O+CO+M reaction in the photoreactor at CCAR (University of Copenhagen) where reagents and contaminants are monitored on-line by FTIR spectroscopy. This study combined with the analysis of the spectral distribution of the employed lamps and isotope kinetic modeling lead to a complete re-interpretation of previous experiments. We conclude that available measurements are more compatible with the hypothesis that there is no mass-independent isotope fractionation in the O+CO reaction. We propose that all observations can be completely explained by an isotope transfer from ozone, involving photolytic production of O(1D) that in turn leads to OH radicals, which then rapidly form CO2 from reaction with CO. We also present a method to produce pure ozone samples and derive an upper limit on nitrogen oxide contaminations based on mass spectrometer measurements. These values will serve as benchmarks values for future studies of ozone absorption cross sections in the IR and UV.

Ce travail de thèse a porte sur l'évaluation de la qualité de l'air sur l'aéroport Paris-Charles- De-Gaulle. L'objectif était d'évaluer l'impact de l'activité aéroportuaire à l'échelle locale et régionale. Cette étude s'est centrée sur les observations à long terme des concentrations des oxydes d'azote (NOx), d'ozone (O3) et des hydrocarbures. Nous avons quantifié la contribution de l'activité aéroportuaire sur les concentrations des NOx observées sur les stations CDG-nord et CDG-sud. Les résultats ont montré que cette contribution était de 18% (12 µ g.m-3) sous un vent du sud et de 47% (25 µ g.m-3) sous un vent du nord. Cette analyse a été réalisée à partir de 3 ans de mesures (2005-2007). Les concentrations des NOx ont également été analysées à l'aide d'un modèle neuronal. Ce modèle a été construit pour estimer les concentrations des NOx en fonction de paramètres météorologiques (direction du vent, vitesse du vent, température, hauteur de la couche limite) et temporels (jour de l'année, heure du jour et la différence entre les jours de la semaine et du week-end). Le modèle a permis d'estimer les concentrations des NOx pour des scénarios ponctuels. Des campagnes de mesures ciblées sur les hydrocarbures ont été mises en oeuvre au cours de cette thèse. Elles ont permis de caractériser la spéciation des hydrocarbures émis par les moteurs d'avion. Les résultats ont montré que cette spéciation était similaire de celle observée pour les véhicules diesel. Ceci ne permet pas d'établir clairement un profil caractéristique permettant de distinguer les émissions des avions de celles de véhicules. La spéciation des hydrocarbures sur la plate-forme a également été évaluée. Les résultats ont montré que la spéciation des hydrocarbures observée sur la plate-forme est comparable à celle observée en milieu urbain et dans d'autres milieux aéroportuaires. Par ailleurs, les concentrations moyennes observées étaient typiquement de l'ordre de celles observées dans une atmosphère urbaine. L'estimation de l'impact des activités aéroportuaires à l'échelle régionale a fait l'objet d'une étude préliminaire à l'aide d'un modèle de chimie-transport, CHIMERE. Cette étude a permis d'évaluer l'étendue spatiale de l'impact de l'activité aéroportuaire pour deux épisodes. Ces épisodes correspondent à un épisode de pollution estival à l'ozone et hivernal au NO2. Les simulations ont indiqué une contribution inférieure à 5µ g.m-3 à une quinzaine de kilomètres sous le vent de l'aéroport

Prior to full-scale implementation of process modifications at the Brantford WTP, a pilot-scale treatability study was conducted to investigate intermediate ozonation/AOP and to determine the most suitable granular media (anthracite, GAC, and Filtralite®) for deep-bed biological filtration. The primary objectives of this research were to provide insight into the destruction of natural and synthetic organics and assess ozonated and halogenated DBP formation. Ozone alone was unable to achieve the 1-log removal target for geosmin or MCPA, unless disinfection-level dosages were applied. No improvement was observed when adding hydrogen peroxide. A major obstacle to the implementation of ozonation in bromide-laden source waters is the formation of bromate. There is a direct correlation between ozone dose and bromate formation and by applying ozone dosages at disinfection levels, bromate is likely to exceed regulatory limits. However, adding hydrogen peroxide reduced the amount of bromate formed, and in most cases levels fell below regulatory limits. A linear correlation was established between bromate inhibition and increasing H2O2/O3 ratio at constant ozone dose. Amongst the three filtration media investigated, only GAC achieved 1-log removal for geosmin and MCPA. The superiority of GAC over anthracite and Filtralite® was attributed to its adsorption affinity. Filtralite® and anthracite media were both ineffective for MCPA removal due to its non-biodegradable nature under conventional water treatment conditions. At a 1 mg/L-ozone dose, GAC and Filtralite® filters achieved a 1-log geosmin removal. In contrast, a 1.44 mg/L ozone dose was required to meet this target with anthracite. The tandem of ozone followed by biological filtration was very effective for the control of distribution system TTHM production regardless of filter media, with levels well below current and anticipated provincial regulatory limits. The combination of intermediate ozonation followed by deep-bed biological filtration is well suited for treating Grand River water. Scale-up considerations include pairing the proper filter media to the size of the ozone generator. The best two treatment scenarios were: Option 1: select GAC media and size the ozone generator to produce a 1 mg/L dose. Option 2: select anthracite media and size the ozone generator to deliver a 2 mg/L dose.

Research in the use of ozone in water treatment conducted by many authors support the idea that the nature and characteristics of natural organic matter (NOM) present in raw water determines the efficiency of ozonation in water purification. An ozone contact chamber was designed and made to allow pre-ozonation of water to take place. The concentration of ozone in the chamber was determined using the Indigo method. For the duration of one year, water samples were collected from four different sampling sites and analyzed to determine their overall ecological status with regard to several variables such as pH, chlorophyll-a, SAC254, turbidity, DOC, algal species composition and sum of NOM. Two dams sites and two riverine sites were chosen, Hartbeespoort Dam (a hyper-eutrophic impoundment), Boskop Dam (a mesotrophic impoundment), Midvaal Water Company at Orkney and Sedibeng Water at Bothaville. The samples were treated in Jar Tests with FeCI3 and the same variables were measured. Preozonation followed by Jar Tests was performed on each sample at twoconcentrations of ozone and the variables were measured to examine the efficiency of ozonation. In general, the ph was high and stayed the same for all the samples and for all the treatments. DOC was variable and showed no relationship to any other variable or to the treatments. Hartbeespoort Dam was found to be a eutrophic impoundment characterized by high algal bloom of the cyanobacteria Microcystis sp., Turbidity, SAC254, and the sum of NOM were lower than for the riverine sites but higher than for Boskop Dam. The NOM constituted more intermediate molecular weight(1MW)and low molecular weight (LMW) fractions than the riverine sites. Ozone was effective in reducing chlorophyll-a, turbidity and SAC254 from Hartbeespoort Dam, but the presence of large numbers of algal cells interferes with its efficiency. Release of cell-bound organics after ozonation can lead to increases instead of decreases in these variables. Jar Test results demonstrate that ozonation improves water quality when compared to conventional treatment although the interference of algal cells can alter results. Boskop Dam is a mesotrophic impoundment characterised by low productivity, low SAC254, tow turbidity and low sum of NOM. However, it has a large portion of the LMW fraction of NOM present. This LMW fraction affects the treatment process as this fraction is not acted upon by ozone. Therefore it was found that ozonation did not improve the quality of the water when compared to conventional treatment. The two riverine sites, Midvaal and Sedibeng were similar to each other. Both sites had high algal productivity with high chlorophyll-a values indicative of algal blooms observed at certain times. These blooms consisted either of members of Bacillariophyceae or Chlorophyceae. High turbidity and SAC254 was observed during the rainy season and was related to the high percentage HMW and IMW fractions of NOM present. There was correlation between the turbidity and SAC254 of these sites leading to the assumption that the turbidity of the river is due to the presence of HMW humic fractions of NOM. Ozonation was effective in improving water quality with respect to turbidity, SAC254 and chlorophyll-a removal, both on its own and after conventional treatment when combined with a coagulant. However, the species of algae present affects ozonation as members of Bacillariophyceae are not affected by the actions of ozone because of the presence of a silica frustule whereas members of Chlorophyceae are easily removed by ozone. In general, ozone acts upon the HMW and LMW fractions of NOM causing them to breakdown into smaller fractions. Ozone has no effect on samples that have a high percentage of the LMW fraction of NOM. This LMW fraction is more readily removed by conventional treatment than by ozonation. The presence of large numbers of algal cells as well as the species of cells can negatively affect the treatment process with regard to ozone. / Thesis (M. Environmental Science (Water Science))--North-West University, Potchefstroom Campus, 2007.

n-type binary compound semiconductors such as InN, InAs, or In2O3 are especial because the branch-point energy or charge neutrality level lies within the conduction band. Their tendency to form a surface electron accumulation layer prevents the formation of rectifying Schottky contacts. Utilizing a reactive sputtering process in an oxygen-containing atmosphere, we demonstrate Schottky barrier diodes on indium oxide thin films with rectifying properties being sufficient for space charge layer spectroscopy. Conventional non-reactive sputtering resulted in ohmic contacts. We compare the rectification of Pt, Pd, and Au Schottky contacts on In2O3 and discuss temperature-dependent current-voltage characteristics of Pt/In2O3 in detail. The results substantiate the picture of oxygen vacancies being the source of electrons accumulating at the surface, however, the position of the charge neutrality level and/or the prediction of Schottky barrier heights from it are questioned.

Persistent organic pollutants (POPs) are organic compounds of anthropogenic origin that have been linked to the development of cancer, neurobehavioural impairment, and immune system biochemical alterations. These chemicals have various industrial applications as well as acting as pesticides. Dioxins and furans are some of these compounds that are unintentionally produced in combustion and industrial processes. By definition these compounds have 4 common qualities: they are highly toxic, they are resistant to environmental degradation, they are introduced into the air and water where they travel long distances, and they accumulate in fatty tissues. Photochemical degradation is a method that has been extensively researched in the last few decades. In the aqueous phase it has already been shown to be able to degrade a number of refractory organics, such as dioxins and furans. The ultimate products of this process tend to be carbon dioxide, water, and mineral anions. Air phase work has been also gaining attention in recent decades as a possible alternative to incineration methods in air pollution control. The advantages of photochemical degradation processes are that they can be initiated at low temperatures, are relatively low cost compared to incineration processes, environmentally benign, and have the potential for quick and complete degradation of organic compounds. The main aim of the research is to investigate the photochemical degradation potential of PCDD/ PCDFs in gaseous air streams as a potential air pollution control technology. In order to do this, the photodegradation reaction kinetics were determined for chlorobenzene as a suitable surrogate for PCDD/PCDFs. Three different photodegradation schemes were employed: direct photolysis, UV/O3, and UV/H2O2. In addition, ozonolysis reaction rates were also determined to evaluate the effects of on the overall photodegradation rates for the UV/O3 process. Factors such as humidity levels and temperature were investigated to determine their effects on degradation rates. Temperature and humidity were not greatly influential on the degradation rates of direct photolysis. The degradation rate of chlorobenzene at a temperature of 100°C and high humidity was noticeably reduced, but unchanged at the 10% RH and 60% RH levels for all temperatures. Ozonolysis of chlorobenzene was negligible at 30°C for all humidity levels. Ozonolysis reactions at the 60°C and 100°C levels were higher than direct photolysis rates and in the 100°C case exceeded the UV/O3 degradation rates. Ozone coupled with UV experiments proved to be the most destructive at the low temperature of 30°C and molar ratio of 10:1 ozone to chlorobenzene. There was a clear and positive relationship between the amount of ozone present in the reactor and the degradation rate. At lower ozone to chlorobenzene molar ratios the degradation rates were not much higher than those for direct photolysis of ozone. The 5:1 molar ratio saw a significant increase in degradation rates over the photolysis rates. The fastest degradation rate was achieved for the 10:1 molar ratio and high humidity, which was over 10 times the rate of direct photolysis. In addition, humidity had a noticeably significant positive effect in these reactions. The effect of temperature on the UV/ozone reaction scheme was determined for the 5:1 ozone to chlorobenzene ratio. Temperature had an interesting effect on the degradation rates at higher temperatures. As the reactor temperature increased, the degradation rates from ozonolysis and UV/O3 began to converge at 60°C, ultimately leading to the ozonolysis reaction being faster than the UV/O3. Exploratory experiments for the H2O2 scheme were performed. H2O2 had a positive influence on the degradation rate of chlorobenzene and was about 26% higher than the direct photolysis rates. However for similar conditions, the UV/O3 process had higher degradation rates as was expected from the difference in absorption values between ozone and hydrogen peroxide.

Grid-type flight patterns at an altitude of 30 m were executed in the summer of 1991 by the Canadian Twin Otter flux research aircraft over a 15 km x 16.5 km agricultural area, as part of the San Joaquin Valley Air Quality Study/California Ozone Deposition Experiment (SJVAQS/CODE). Fast-response on board sensors for turbulence, temperature and gas concentrations permitted the spatial mapping of fluxes of momentum, sensible heat, moisture, CO$ sb2$ and ozone. Flux maps were produced in the form of GIS-interpolated 1 km averages, and in the discrete form of those coherent structures of the turbulent process, intermittent in time and space, which dominate the exchange of scalars between the ground and the atmosphere. The magnitude of surface-related mesoscale contributions to the flux was also quantified. Flux observations were compared against radiometrically observed surface temperatures and vegetation indices (NDVI), observed from aircraft and satellite (NOAA AVHRR), and surface characteristics from ground surveys. / Flux maps showed the expected correspondence between greenness, evapo(trans)ration (ET) and CO$ sb2$ exchange. Discrepancies between ozone flux maps and maps of greenness, ET or CO$ sb2$ were more pronounced than would be consistent with the hypothesis of stomatal control of ozone uptake. More insight into control mechanisms on ozone exchange is gained by an examination of the spatial coincidence between transporting structures for the various scalars (heat, moisture, CO$ sb2$ and ozone), through the Jaccard coefficient of co-location (J), which showed a lower value ($ rm0.3<J<0.6$) for coincidence in transfer between ozone and moisture than between moisture and CO$ sb2$ ($ rm0.5<J<0.8$). Analysis of J over the various land-use and crop-types in the test area, opens a door to a more differentiated understanding of the physical and physiological driving forces behind ozone uptake by soil and vegetation.

Die derzeit angewendete Formalinbegasung von Bruteiern zur Keimreduktion stellt ein wichtiges Mittel zum Schutz des Verbrauchers vor dem Eintrag der Salmonellose aus der Geflügelindustrie in die Lebensmittelkette dar. Jedoch verlangt sein kanzerogenes Potenzial die Suche nach einer ebenso effektiven und einfach zu praktizierenden, aber weniger gesundheitlich bedenklichen alternativen Methode. In dieser Arbeit wurde die Eignung einer in ovo-Ozonbegasung zur Bruteidesinfektion hinsichtlich ihrer Auswirkung auf die Embryonalentwicklung untersucht. Dafür wurden befruchtete Eier vor ihrem Einsatz in den Brüter mit unterschiedlichen Ozonkonzentrationen zwischen 0,5% bis >5,0% (wt/ wt O3 in O2) bei einer relativen Luftfeuchte von 70% in einer Laborkammer begast. Die verwendeten Ozonkonzentrationen wurden dabei in drei Konzentrationsgruppen eingeteilt: hoch (2,8% bis 5,0%), mittel (1,1% bis 2,5%) und niedrig (0,5% bis 1,0%). Nach Erreichen der Zielkonzentration blieben die Eier für eine definierte Einwirkzeit (EWZ) zwischen 0 bis 24 h in der Kammer. Am Bruttag (BT) 18, 19 oder 20 wurden die Überlebensrate (ÜLR), Gewicht und Länge erhoben sowie histologische Untersuchungen der Organe Herz, Leber, Milz und Niere vorgenommen. Bei vier Versuchen erfolgte zusätzlich die Untersuchung am BT 6 und BT 12. Insgesamt wurden 13 Versuchsreihen mit Begasungen in der Laborkammer in den drei genannten Konzentrationsgruppen durchgeführt. Des Weiteren sollte die Übertragbarkeit der ermittelten Ergebnisse auf eine großtechnische Lösung, durch die Anwendung in einer projektintern entwickelten Prototyp-Kammer überprüft werden. Die Konzipierung dieses Prototyps folgte den technischen Gegebenheiten unter Einbeziehung der ermittelten Ergebnisse zur Embryotoxizität, zur Effektivität der Keimreduktion sowie der Veränderung der Eiinhaltsstoffe. Im Prototyp wurde daher die Begasungskonzentration von 0,7% Ozon bei einer EWZ von 2 h angewendet und in 2 Versuchsreihen hinsichtlich ihrer Auswirkungen auf die Lebensfähigkeit und die morphologische Entwicklung getestet. Um zusätzlich eine Aussage treffen zu können, welche Wirkung eine hohe Ozonkonzentration bei der Applikation während der Bebrütung zur Folge hat, wurde in zwei weiteren Versuchsreihen jeweils am BT 3, 4 und 5 eine Ozondosis von 5,0% in Kombination mit 1 h EWZ appliziert. Nach der Entnahme der Embryonen am BT 6 bzw. BT 8 erfolgte die morphologische Untersuchung. Aus der vorliegenden Arbeit wird zusammenfassend geschlussfolgert:  Ozon besitzt einen dosisabhängigen Effekt auf die ÜLR: je höher die Dosis, desto geringer die Überlebensrate. Bei niedrigen Ozonkonzentrationen zwischen 0,5% und 1,0% kommt es zu ÜLR von 90% und 100%.  Die Einwirkzeit stellt einen wichtigen Einflussfaktor auf die Überlebensrate dar. Eine Kombination einer hohen Ozondosis mit langer EWZ hat eine höhere Embryomortalität zur Folge, als eine hohe Ozondosis ohne EWZ. Eine erhöhte Mortalitätsrate zeigt sich auch bei der Kombination einer mittleren Ozondosis mit einer langen EWZ. Keinen Einfluss zeigt sie bei der Kombination mit einer niedrigen Ozonkonzentration.  Ozonierte Embryonen zeigen dosisabhängig eine geringere Längen- oder Gewichtsentwicklung im Vergleich zur Kontrollgruppe. Signifikante Gewichts- und Längenunterschiede lagen nur vereinzelt bei der Begasung mit hoher Ozonkonzentration vor.  Pathohistologische Befunde an Organen, die mit einer Ozonbegasung in Zusammenhang gebracht werden können, konnten nicht erhoben werden.  Die Versuche zur Begasung während der Organogenese wiesen nicht auf ein teratogenes Potenzial von Ozon hin. Korrespondierend mit den Ergebnissen der Begasung am BT 0 zeigte sich ebenfalls eine deutliche Embryotoxizität.  Die Wirkung von Ozon folgt einem Alles-oder-Nichts-Prinzip: entweder die Schädigung ist so stark, dass es zu keiner Entwicklung mehr kommt, oder aber der überlebende Embryo bzw. Fetus zeigt ein phänotypisch normales Aussehen.  Mit den vorgestellten Untersuchungen konnte bewiesen werden, dass bei einer in ovo-Begasung von befruchteten Hühnereiern am Bruttag 0 mit einer niedrigen Ozonkonzentration von 0,5% bis 1,0% in Kombination mit einer mittleren und geringen EWZ keine teratogenen oder embryotoxischen Veränderungen zu erwarten sind.  Aus diesen Befunden ergibt sich ein unbedenklicher Einsatze von Ozon als alternative Methode zur Bruteidesinfektion. Die Voraussetzung dafür ist, dass die großtechnische Lösung die Anwendung von 1,0% Ozonkonzentration in Kombination mit 2 h EWZ ermöglicht, um eine sehr gute ÜLR, Entwicklung und eine 100%ige Inaktivierung des in Legehennenbeständen vorherrschenden Serovars Salmonella Enteritidis zu gewährleisten.