Inkjet printing technology became a popular technology for printing digital photographs in the last decade. There is a big variety of both original and alternative (cheaper) inks and print media for the consumers. But there is a question if the cheaper material provides also comparable printout quality. For this reason, it is important to test the properties of such inkjet printouts. There are several ways how to test the lightfastness of the printouts: long term storage under environmental conditions, or short, accelerated ageing tests. The stability of printouts is affected by many factors, such as ink-receiving layer, ink composition, UV and visible light intensity and air pollutants concentration in the environment. Some inkjet printouts exposed to light usually undergo surprisingly fast fading, but light is not the only dangerous condition for inkjet printout. The two types of test targets printed with dyebased inkjet inks on various paper types were subjected to both accelerated test in a xenon test chamber and light and environmental pollutants long-term test in a sunny indoor corridor. The values of light intensity were continuously monitored and samples properties were regularly measured with a spectrophotometer. Another type of testing included accelerated ozone ageing of inkjet dyes. The colour gamuts and gamut volumes were calculated from collected spectral data. Total colour difference E*ab was also evaluated, its increase served as a tool for finding the formal printout degradation rate constant. It was found out that the dyes in ink-receiving layers of printouts underwent significant degradation in all tested conditions. The degradation rate depended on the type of used print media. The reciprocity behaviour of printouts was also studied. Recent inkjet printouts testing miss some actual ISO norm which should show the way of effective lightfastness evaluation. One of the main aims of this work was to find some new and alternative ways of inkjet printouts lightfastness evaluation. The method of printed inks concentration determination from the test charts spectrophotometric measurements was also proposed.

Gegenstand der Arbeit ist die Untersuchung der Anwendbarkeit stochastisch-deterministischer Modelle für die räumliche und zeitliche Vorhersage der Ozonkonzentrationen in Sachsen. Zu diesem Zweck werden die Messwerte des sächsischen Landesmessnetzes von 1995 bis 1999 einer eingehenden statistischen Analyse (deskriptive Analyse, geostatistische Analyse, Zeitreihenanalyse) unterzogen. Bei diesen Analysen werden Repräsentativitätsunterschiede der einzelnen Stationen (städtisch/ländlich) deutlich, die bei Verwendung aller Daten zu einem sehr hohen Nuggeteffekt führen. Um ein realistischeres Bild des Nuggeteffektes zu erhalten, wurde die jeweils am stärksten verkehrsbeeinflusste Station in derselben Stadt aus der Variogrammberechnung ausgeschlossen. Durch die Forschungsarbeit wird gezeigt, dass die Ozonwerte auch nach der Eliminierung räumlicher und zeitlicher Trends eine ausreichende räumliche Autokorrelation besitzen. Schließlich werden geostatistische und zeitreihenanalytische Modelle für die räumliche und zeitliche Vorhersage der sächsischen Ozondaten entwickelt und ihre Genauigkeit überprüft.

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.

Dans ce travail nous avons étudié des réactions chimiques sur la surface de deux métaux : le platine et l'or, en utilisant la microscopie ionique à effet de champ électrique (FIM) et la spectrométrie de masse de désorption par champ pulsé (PFDMS). En complément de ces données expérimentales, nous apportons des résultats obtenus par la théorie de la fonctionnelle de la densité (DFT). La taille et la morphologie de nos échantillons font qu’ils sont de bons modèles de grains de phase active dans un catalyseur réel. Sur le platine nous avons observé l'interaction du monoxyde d'azote. En présence d'un champ électrique, la dissociation du NO est promue, laissant sur la pointe une couche d'oxygène que l'on peut titrer par la suite avec du NO pour former du dioxyde d'azote. L'interaction de l'hydrogène avec une pointe de platine est différente en fonction de la température. A basse température (<200 K), l’hydrogène met en image la pointe avec un assombrissement de petites régions de la pointe. A partir de 200 K, l'hydrogène induit une transformation de la pointe : les faces denses s'élargissent au détriment des faces rugueuses, avec une rangée d'atomes le long des lignes de zone [100] et le pôle central passe d’une forme circulaire à une forme carrée. L'hydrogène est supposé être à l'état atomique sur la surface; sous sa forme moléculaire, il ne contribue qu'à la mise en image. C’est sous sa forme atomique qu’il contribue aux transformations observées. La réaction NO+H2 sur le platine conduit à l'observation d'instabilités cinétiques pour des pressions et températures données. Les régions d'amorçage ont été identifiées comme étant tout ensemble de sites de cran situé le long des lignes de zone [100]. L'observation de phénomènes oscillants n'est pas liée exclusivement à une morphologie de type polyédrique : il est possible d’observer ces instabilités cinétiques sur des pointes de rayon de courbure différent, ces pointes ne subissent pas nécessairement un changement de morphologie. L'analyse chimique au cours de la réaction a révélé la présence d'oxydes de surface ce qui nous a conduit à penser que la surface du catalyseur de platine doit être oxydée plutôt que de rester à l'état métallique. Une étape intermédiaire dans le mécanisme de site vacant a été proposée pour permettre de rendre compte de l'apparition de phénomènes oscillants. L’étape déterminante est la décomposition du monoxyde d’azote adsorbé à la surface. L’apport d’hydrogène atomique nécessaire à la formation d’eau n’est pas une étape lente, au contraire l’hydrogène semble être largement présent sous forme atomique. L’influence du champ électrique reste important, ce qui pourrait expliquer les différences de gammes de température auxquelles d’autres groupes et le nôtre observons des oscillations. L'étude de l'interaction du CO seul sur l'or a été motivée par l'observation de la réaction CO+O2 sur pointe d'or. Sous nos conditions expérimentales, il est possible de former des mono- et dicarbonyles d’or sous forme cationique. En présence d'un champ électrique, la formation de carbonyles d'or est promue au niveau des sites de cran de la surface. Les résultats obtenus par DFT sont concordants avec les résultats expérimentaux. A l'instar du Pt, nous avons étudié l'interaction du monoxyde d'azote sur pointe d'or. Nous avons observé la formation de protoxyde d'azote et d'un dimère de monoxyde d'azote. Le mécanisme de formation de ces espèces reste encore inconnu. Une couche d'oxygène adsorbée à la surface peut être titrée par du NO en formant du dioxyde d'azote. En présence d'oxygène seul sur une pointe d'or sans champ électrique, les spectres de masse ne révèlent que la présence d'oxygène moléculaire. En présence d'un champ électrique, il est possible de détecter de l'oxygène atomique sans toutefois avoir la formation d'un oxyde d'or. Il est possible de former de l'ozone à partir d'une pointe recouverte d'oxygène atomique en présence d'oxygène moléculaire gazeux. Les calculs par DFT nous laissent à penser que la formation du cation O3+ ne se fait pas à la surface mais à proximité. Ils montrent entre autres que le champ électrique déstabilise l'oxygène atomique, ce qui pourrait le pousser vers des régions où l'effet du champ est le moins intense (la tige de la pointe).

Die Siliciumauflösung in Flusssäure-Wasserstoffperoxid- und Flusssäure-Ozon-Lösung ist aufgrund der, aus der Oxidation des Siliciums, formal resultierenden Reaktionsprodukte Wasser und Sauerstoff interessant. Der Auflösungsprozess, speziell die Oxidation des Siliciums / Elektronenlochinjektion ins Siliciumvalenzband, wird – verglichen mit anderen Ätzsystemen für Silicium – massiv kinetisch gehemmt. Ätzprozesse auf Basis dieser Mischungen sind hinsichtlich der geringen bzw. moderaten erzielbaren Siliciumabtragsraten (rSi < 0,02 nm s-1 mit Rissaufweitung in Flusssäure-Wasserstoff-peroxid-Lösungen bzw. rSi < 0,61 nm s-1 mit Oberflächenpolitur in Flusssäure-Ozon-Lösungen) wenig effektiv. Eine Erhöhung der Siliciumabtragsraten gelingt prinzipiell durch die Erhöhung der Konzentrationen siliciumoxidierender Spezies in der Silicium / Elektrolyt-Grenzfläche oder durch Zufügen geeigneter grenzflächenaktiver Elektronenüberträgerspezies. In stark sauren Lösungen wird der Elektronentransfer zusätzlich durch stabilisierende Wasserstoffaustauschprozesse inhibiert. Die Mischungen sind zur Reinigung von Siliciumwaferoberflächen oder feinteiligem Silicium geeignet.

Stora mängder receptbelagda- och receptfria läkemedel brukas årligen. Farmaceutiska föreningar såsom exempelvis preventivmedel, antibiotikum och smärtstillande läkemedel når reningsverk via urin och fekalier. Traditionella reningsverk saknar förmågan att helt reducera dessa föreningar och de släpps ut via det utgående vattnet till en recipient där de kan medföra en negativ påverkan i miljön. Duvbackens reningsverk i Gävle har en traditionell uppbyggnad och det behandlade spillvattnet släpps ut i Inre Fjärden. Syftet med denna studie är att utifrån Duvbackens avloppsreningsverks förhållanden föreslå en rekommenderad kompletterande reningsmetod för att reducera läkemedelsrester ifrån spillvattnet.   För att kunna föreslå en kompletterande reningsmetod har en provtagning efter läkemedelssubstanser på det inkommande och det utgående spillvattnet genomförts i Duvbackens reningsverk. Detta för att se vilka substanser reningsverket reducerar och vilka som släpps ut i Inre Fjärden.  En litteraturstudie har genomförts där aktivt kol och ozons reduktionsförmåga av läkemedelsrester granskats, samt vart i reningsverket de bör implementeras. Kostnader av aktivt kol och ozon har ställs i förhållande till varandra genom en ekonomisk undersökning.   Duvbackens reningsverk är dimensionerat för 100 000 personekvivalenter och är beläget mellan stadsdelarna Brynäs och Bomhus i Gävle. Reningsverket använder sig av mekanisk, biologisk och vid behov kemisk rening. Resultaten från provtagningen visade att av de 22 läkemedelssubstanser vilka granskats reducerades sex substanser med mindre än 45 % och två substanser fick en förhöjd halt efter de passerat Duvbackens reningsverk.   Både ozon och aktivt kol har i tidigare pilotförsök visat god förmåga att reducera läkemedelssubstanser från avloppsvatten. Variation av reduktionsgrader har visats bero på kolförbrukning och dosering av ozon. En skillnad mellan de kompletterande reningsmetoderna är att aktivt kols reduktionsförmåga försämras med tiden medan ozon har en mer konstant reduktion av läkemedelssubstanser.   Ozon bör implementeras efter slutsedimenteringen följt av ett sandfilter för att reducera reaktiva biprodukter. Vid användning av aktivt kol bör reningsmetoden implementeras efter slutsedimenteringen, då det är av stor vikt att spillvattnet inte har för höga halter av suspenderade ämnen som mättar kolet. När aktivt kol och ozons kostnader jämförts under samma förhållanden har aktivt kol visats vara marginellt dyrare. Energikostnader utgör de stora kostnaderna för ozonrening medan kolförbrukningen visats utgöra den stora kostnaden för rening med aktivt kol. / Large amounts of prescription- and non-prescription pharmaceutical drugs are used annually. Pharmaceutical compounds such as contraception, antibiotics and analgesic drugs end up in sewage treatment plants via urine and feces. The traditional sewage treatment plant lacks the ability to completely reduce pharmaceutical compounds and they are emitted via efflux to a recipient, where they can have a negative impact on the environment. The sewage treatment plant Duvbacken in Gävle has a traditional structure and the treated effluent end up in Inre Fjärden. The purpose of this study is to recommend a complementary treatment method to reduce pharmaceutical compounds based on the sewage treatment plant Duvbacken’s circumstances.   In order to recommend a complementary treatment method samples of the incoming and outgoing efflux have been tested for pharmaceutical substances. The samples were taken to see what substances the sewage treatment plant reduces and what substances end up in Inre Fjärden. A literature review was conducted to examine activated carbon and ozone’s ability to reduce pharmaceutical compounds, it also researched where the treatment methods should be implemented. An economical investigation was done to show the costs for activated carbon and ozone in relation to each other.   The sewage treatment plant Duvbacken in Gävle is constructed for 100 000 persons and is located between the suburban areas Brynäs and Bomhus. The sewage treatment plant uses mechanical, biological and if necessary chemical treatment. The results from the samples of the 22 substances that were examined showed that six pharmaceuticals were reduced by less than 45 % and two substances had an increased concentration after treatment in the sewage treatment plant.   Both ozone and activated carbon have in previous studies shown good ability to reduce pharmaceutical substances from the municipal efflux. Variations in the ability to reduce pharmaceuticals depends on carbon consumption and ozone dosage. One difference between the complementary treatment methods are that activated carbons ability to reduce pharmaceuticals decreases with time, while ozone has a more constant reduction.   Ozone should be implemented after the traditional treatment followed by a sand filter to reduce reactive byproducts. Activated carbon should also be implemented after the traditional treatment due to an efflux with high content of suspended substances can saturate the carbon. When the costs of activated carbon and ozone are compared under the same circumstances it has been shown that activated carbon is marginally more expensive. The energy use represents the major costs for ozone treatment while carbon consumption has shown to be the major cost for activated carbon.

Regarding the vegetation, the most affected areas by high levels of surface ozone (O3) are the mountain ridges. Our study has been carried out in the Jizerske hory Mts. High O3 levels together with the convenient environmental conditions for stomatal conductance could be a threat for the health of recovering ecosystems in this area. The aims of this study was both to assess the influence of O3 on vegetation in the Czech mountains and to provide recommendations and outlooks for possible future using of relatively new methods (visible symptoms and stomatal O3 flux modelling) used for O3 impact assessment on native vegetation in the field; that means physiologically relevant methods for the determination of O3 influence. During 2006 and 2007, O3-like visible symptoms were assessed on the leaves of seven species at four sites. Symptoms on only two species (Fagus sylvatica L. and Rubus idaeus L.) have been determined as O3-induced. To our knowledge, it is the first study in the Czech Republic in which the O3-like symptoms on native plants have been verified by the Ozone Validation Centre for Central Europe. Our results based on O3-induced symptoms indicate that ambient O3 is likely to have a much lower impact than expected, considering the measured O3 concentrations (measured with passive samplers) and...

Die antioxidativen Enzyme Katalase (KAT), Glutathion-Peroxidase (GPX), Glutathion-Reduktase (GR), Superoxid-Dismutase (SOD) und Glutathion-S-Transferase (GST) sind an der intrazellulären Abwehr von oxidativem Stress beteiligt. Diverse Arbeitsgruppen fanden eine Hochregulation der antioxidativen Enzyme (AOEs) nach Exposition auf Ozon. In der vorliegenden Studie sollte an einem von Schierhorn und Mitarbeitern entwickelten Kulturmodell der nasalen Mukosa des Menschen untersucht werden, ob Aktivitätsänderungen der AOEs nach Ozonexposition in vitro zu verzeichnen sind. Zu diesem Zweck wurde die nasale Mukosa von 67 Patienten, die sich wegen nasaler Atmungsbehinderung einer Conchotomie unterzogen hatten, 24 Stunden bei 37 °C und 5% CO2 kultiviert und parallel unter den selben Bedingungen einer zusätzlichen Ozonkonzentration von 120 ppb ausgesetzt. Tendenzielle Aktivitätsänderungen durch Ozon ließen sich bei der GPX (13.8 auf 17.7 mU/mg Protein, 28% Steigerung) und der SOD (8.4 auf 9.7 U/mg Protein, 15% Steigerung) feststellen. Diese Aktivitätszunahmen wiesen jedoch keine Signifikanz auf. Aktivtätsänderungen bei KAT, GR und GST durch die Ozonexposition wurden nicht gefunden. Alter der Patienten, Geschlecht und Zigarettenrauchen nahmen den Ergebnissen dieser Studie nach keinen Einfluß auf die Regulation der AOEs nach Ozonexposition. Die Deletion der Glutathion-S-Transferase M1, die bei etwa 50% der mitteleuropäischen Bevölkerung zu finden ist, veränderte die Regulation der SOD nach in vitro Ozonexposition. Die GST-defizienten Patienten dieser Studie beantworteten die Ozonexposition mit einer signifikanten Hochregulation der SOD (p / Antioxidant enzymes as catalase (CAT), glutathione peroxidase (GPX), superoxide dismutase (SOD) and glutathione S-transferase (GST) are thought the primary cellular defense mechanism against reactive oxygen species. Ozone, a highly reactive oxidant, is known to cause respiratory symptoms at ambiental doses. A number of studies have shown the mucosa of the respiratory tract to be the first target site of ozone toxicity. Other animal studies demonstrated an upregulation of mucosal antioxidant enzymes after ozone exposition. Concerning to the antioxidant defense mechanisms of the human nasal mucosa no studies are found so far. The purpose of this study was to determine if in vitro ozone exposure of human nasal mucosa results in changes in the activity of CAT, GPX, SOD, GST and glutathione reductase (GR). Nasal mucosa from 67 patients was cultivated in a specially designed in vitro organ culture and exposed to 120 ppb ozone for 24 hours. The results were compared with the histamin release which is known to be upregulated from human nasal mucosa after ozone exposition (60-200 ppb).

Background: The negative effects of air pollution on morbidity and mortality have been known since the mid 20th century. The two most well known examples are the Meuse Valley disaster in the 1930’ies and the London black fog in December 1952. Whilst there are numerous epidemiological studies, in which associations between morbidity and mortality and high levels of pollutants have been reported, the underlying mechanisms are not clear. Two of the main air pollutants are particulate matter (PM) mostly emanating from diesel exhaust (DE), and ozone, both of which are highly oxidative. Exposure to DE has resulted in adverse effects both in the respiratory tract and in the cardiovascular system. High ozone levels have also been shown to be associated with increased admissions to hospital for respiratory as well as cardiovascular conditions. The main aim of this thesis was to investigate the respiratory and cardiovascular effects of a combination of exposures to ozone and DE. DE generated during the urban part of the standardized European Transient Cycle (ETC) was compared to DE generated by an idling engine. It was also evaluated whether an acute exposure to ozone would have any effects on the cardiovascular system as assessed by venous occlusion forearm plethysmography and heart rate variability (HRV). In addition, fraction of exhaled nitric oxide (FENO) was evaluated as a potential marker for acute exposure to ozone or DE. Methods: Four double-blind randomized cross-over exposure studies were conducted to investigate the effects of ozone and DE on both the respiratory tract and the vascular function in healthy volunteers. All of the exposures were performed in purposely built “walk-in” chambers with strictly controlled exposures. In the first study, the volunteers were exposed to DE (300µg/m3) generated by an idling engine or to air, for one hour in the morning and to ozone (200 ppb) for two hours in the afternoon. A bronchoscopy with bronchial wash (BW) and bronchoalveolar lavage (BAL) was performed 24 hours after the initial exposure. In study II and III, an assessment of vascular function using venous occlusion forearm plethysmography was performed after an exposure to DE (250 µg/m3) generated under transient running conditions, compared to air exposure (study II) and ozone and air exposure (study III). HRV was assessed under a 24 hour period starting before each exposure (study III). In study IV, FENO measurements were conducted after DE and ozone exposures to investigate whether the previously established airway inflammation would be detectable by this non-invasive method. Results: DE exposure enhanced the established ozone-induced airway inflammation in terms of a pronounced neutrophilia in BW. DE generated under transient running conditions, impaired vascular function in healthy volunteers, whereas exposure to ozone did not. HRV were not altered by exposure to ozone. Exposure to DE caused a significant increase in FENO at the 10  (FENO10) and 50 (FENO50) mL/s flow rates at 6 hours post-exposure, but ozone exposure did not affect FENO at any flow rate or time point. Conclusion: We have tried to mimic real-life exposure to air pollutants. In the first study, an exposure to DE followed by an exposure to ozone in the afternoon resulted in an enhanced airway inflammation, suggesting an additive or synergistic effect, supporting the epidemiological findings of unfavorable effects of the combination of these two air pollutants. DE generated by an engine running at the urban part of the standardized European Transient Cycle impaired two important and complementary aspects of vascular function, the regulation of vascular tone and endogenous fibrinolysis. This has previously been shown with DE generated at idling conditions. This suggests that the mechanisms behind the adverse effects can be found in the properties of the particles and not in the gaseous components. In these studies, exposure to ozone did not impair vascular function in healthy subjects, or cause any alterations in HRV. This suggests that the epidemiological evidence for an increased risk of cardiovascular mortality following acute exposure to ozone might not be totally accurate. Previous controlled exposure studies with ozone have not shown an airway inflammation affecting the endothelium, at least not in the same time-frame as following DE exposure. FENO could possibly be a useful tool for assessing airway inflammation caused by DE, whereas the powerful oxidant ozone did not affect FENO. This suggests that the airway inflammatory effects caused by these two pollutants are regulated via different mechanisms.

In the general part of this diploma thesis are presented technical information collected on the issue of spontaneous decay of ozone in water solution and problems with analytical monitoring of these processes. Particular attention is paid to influence of pH value, bicarbonate and peroxide concentration on ozone decay kinetics. Experimental part is focused on the use of spectrophotometry in the study of chemical reactions associated with the spontaneous decay of ozone in distilled and tap water depending on pH and temperature after saturating of water by ozone prepared from air and pure oxygen. Direct photometry in UV range of spectrum (at 260 nm) was used to monitoring of ozone decomposition kinetics.