This diploma thesis deals with ozone measurement methods, especially focusing on opto-chemical methods, when the color change of the sample is examined. Moreover it deals with dyes that are sensitive to ozone and their degradation kinetics. In the experimental part kinetics of dyes Orange I, Orange II and Indigo carmine is examined, These dyes are prepared in the form of ink of different composition. These inks are applied to diverse substrate materials by the material printing method, further by using a Baker film aplicator and in the end by the screen printing method. The properties of the samples are evaluated as well as factors affecting their degradation.

Dans le vin rouge, les composés phénoliques sont souvent associés à la qualité du produit. Parmi eux, les anthocyanes sont responsables de la couleur du vin rouge et chaque cépage possède un génome spécifique déterminant le profil anthocyanique de chacun. Les pratiques culturales peuvent influencer l’accumulation de ces molécules dans la baie de raisin, tandis que les différentes techniques fermentaires peuvent modifier leur extraction. Les flavanols monomères, oligomères et polymères des pépins et des pellicules contribuent à l’amertume et l’astringence des vins. Pendant la vinification et l’élevage, ceux-ci réagissent avec les anthocyanes modifiant les propriétés du vin. De nombreuses publications concernant les caractéristiques sensorielles des flavanols ont été réalisées, alors que la contribution sensorielle des anthocyanes est encore mal connue. Cette thèse se décompose en deux parties. La première partie s’intéresse à l’étude de l’utilisation d’ozone gazeux comme technique pré-fermentaire sur les cépages rouges Nebbiolo et Barbera après récolte et pendant le passerillage. L’ozone est une technique innovante pour la réduction des contaminations microbiennes et la réduction du dioxyde de soufre. L’influence de cette technique sur les parois cellulaire des pellicules, sur l’extraction, la concentration en flavanols et en anthocyanes pendant la macération a été évaluée. L’étude montre que l’ozone possède un impact sur la macération des raisins, induisant une extraction plus importante des anthocyanes dans le Nebbiolo. En revanche, l’ozone n’influence ni les anthocyanes moléculaires, ni le profil variétal de chaque cépage. Pendant le passerillage, l’inverse a été étudié. L’extraction des anthocyanes dans le Nebbiolo est diminuée. A l’inverse, bien que moins d’anthocyanes soient retrouvées dans le raisin de Barbera, le traitement ne possède aucun impact sur l’extraction de celles-ci. Concernant les flavanols, l’extraction est moins influencée par le traitement à l’ozone. Des différences ont été retrouvées dans le cépage Nebbiolo. Les flavonols sont plus concentrés après le traitement avec l’ozone sur les raisins post-récolte, alors qu’ils diminuent pendant le passerillage. La modification causée sur la paroi cellulaire par l’ozone ainsi que la dureté des pellicules pourraient prédire l’extraction des anthocyanes et des flavanols, grâce à des analyses multi-variées. En conséquence, le traitement avec l’ozone doit être adapté en fonction du cépage et du produit final désiré. Dans la deuxième partie, les anthocyanes des raisins ont été extraites à partir des raisins et ces extraits ont été fractionnés en trois fractions, glucoside, acetyl-glucoside et cinnamoyl-glucoside, par Chromatographie de Partage Centrifuge (CPC) et CLHP (Chromatographie Liquide Haute Performance) préparative. L’évaluation de l’astringence a été réalisée par des analyses de précipitation protéique avec une protéine modèle BSA (Bovine Serum Albumin) et des protéines salivaires, les anthocyanes réagissant avec ces dernières. Les analyses sensorielles et l’évaluation de l’astringence ont été combinées. La concentration en anthocyane diminue après le traitement avec les protéines salivaires, dans l’extrait total et dans les fractions, en particulier les cinnamoyl-glucosides apparaissent comme les plus réactives avec les protéines salivaires. Les seuils de perception gustatifs ont été calculés avec la méthode “Best estimate threshold” dans le vin modèle. Les fractions acétyl-glucosides et cinnamoyl-glucosides, suivies de la fraction glucoside, possèdent des seuils de perception plus bas aux concentrations retrouvées dans les vins. Les descripteurs associés à ces fractions sont l’amertume et l’astringence. Ces résultats démontreraient que les anthocyanes apportent une contribution sensorielle dans la perception du vin en bouche, corrélée à l’acétylation des molécules. / In red wine, phenolic compounds are generally associated with the quality of products. Among them, anthocyanins extracted from skins are responsible for wine colour. The grapevine genomes determine the anthocyanins profiles, but several factors in the vineyard can influence their accumulation, as well as post-harvest techniques can modify their extraction during winemaking. Monomeric, oligomeric and polymeric flavanols from skins and seeds contribute to astringency and bitterness of wine and during winemaking and ageing complexes formation with anthocyanins modifies wine characteristics. Several publications are available to understand flavanols sensory characteristics, whereas anthocyanins role has not consensus in scientific literature. This PhD thesis is composed by two parts. The first part deal with the evaluation of the use of gaseous ozone as post-harvest technique in red wine grapes Nebbiolo and Barbera used on both fresh grape and during withering. Ozone treatment is an innovative technology proved to avoid mycobiota spoilage and preserving from the use of sulphur dioxide. Its influence on flavanol and anthocyanin contents and extractabilities during maceration was evaluated, considering skin cell wall modification. In fresh grape, ozone influenced skin maceration for both the varieties, leading to a higher anthocyanin extraction in Nebbiolo grapes and lower in Barbera. Ozone did not influence the final individual anthocyanin extractability, respecting the varietal anthocyanin fingerprint. During dehydration, opposite trend was found: in Nebbiolo reported no change in the content of total anthocyanins just after ozone-assisted dehydration, but their extraction yield was lower. On the contrary, although lower contents of anthocyanins were found in Barbera grapes no differences in final extractability was found. Regarding oligomeric and polymeric flavanols, their extractability was less affected by the ozone treatment. Only in Nebbiolo, both oligomeric and polymeric flavanol extraction was increased in fresh grape, whereas it is slightly decrease during dehydration. The ozone-induced modification of skin cell wall composition together with skin hardness parameters fitted well in multivariate models to predict anthocyanins, oligomeric flavanols and polymeric flavanols extraction. Therefore, the ozone treatment should be adapted depending on the variety and on the target wine. In the second part, grape anthocyanins were isolated depending on the acylation patterns, i.e. glucoside, acetyl-glucoside, and cinnamoyl-glucoside by a combination of centrifugal partition chromatography (CPC) and preparative-HPLC. Protein precipitation analyses to assess astringency and sensorial analysis were carried out. Anthocyanins reacted with both bovine serum albumine and salivary proteins, in different extent, since higher interaction between anthocyanins and salivary proteins was found with a significative reduction of total extract and fractions glucoside, acetyl-glucoside, and cinnamoyl-glucoside. The latter in particular is the more reactive to salivary proteins. Sensorial analysis was carried out as detection threshold test. Best estimated threshold (BET) of anthocyanins were resulted in wine-range scale, in particular acetyl-glucoside and cinnamoyl-glucoside BET are lower of glucoside threshold, and descriptors reported were astringency and bitterness. These results show that anthocyanins can be detected as in-mouth properties contributors, and the magnitude of their involvement is related to anthocyanins acylation.

L'objectif de cette thèse est d'étudier les phénomènes d'import et d'export de la pollution gazeuse et particulaire au-dessus du Bassin Méditerranéen (BM). Ce travail consiste dans un premier temps à étudier l'évolution de l'ozone (O3) de surface dans un contexte de changement climatique au-dessus du BM entre 2000 et 2100, en exploitant les sorties issues de 13 modèles participant à l'exercice ACCMIP (Atmospheric Chemistry and Climate Model Intercomparison Project). Nous avons montré que l'ozone de surface diminue entre 2000 et 2030 (2100) pour 3 RCPs (Representative Concentration Pathway) : -14% (-38%) pour le RCP2.6, -9% (-24%) pour le RCP4.5 et -10% (-29%) pour le RCP6.0, alors que pour le scénario RCP8.5, l'ozone de surface reste stable au cours du XXIème siècle. Dans un second temps, nous avons identifié les sources et les chemins de transport de l'O3 et du monoxyde de carbone (CO) représentatifs des différentes régions du BM : l'Est, l'Ouest et le Centre entre 2012 et 2014, en utilisant une approche statistique qui combine des observations de surface et des rétro-trajectoires issues du modèle HYSPLIT (Hybrid Single Particle Lagrangian Trajectory). En général, l'O3 et le CO sont transportés, respectivement, depuis l'Europe continentale et l'Europe de l'Est vers le BM. Finalement, nous avons étudié les phénomènes d'import et d'export de la pollution au-dessus du BM, en utilisant le modèle MOCAGE (Modèle de Chimie Atmosphérique à Grande Échelle) et le modèle HYSPLIT, et en exploitant les observations récoltées lors des deux campagnes de mesures TRAQA (TRAnsport à longue distance et Qualité de l'Air) (été 2012) et GLAM (Gradient in Longitude of Atmospheric constituents above the Mediterranean basin) (août 2014) réalisées dans le cadre du programme ChArMEx (The Chemistry-Aerosol Mediterranean Experiment). Nous avons mis en évidence le transport à longue distance des masses d'air enrichies en O3 et l'impact du Mistral sur le mélange des masses d'air. Le bilan d'O3 et de CO a été aussi réalisé sur le BM pour l'année 2012 à partir des simulations du modèle MOCAGE. Les résultats montrent que le CO est importé vers le BM pendant le printemps et l'été alors que l'O3 est importé vers le BM durant la période janvier-juin puis exporté le reste de l'année. / The objective of this thesis is to study the import and the export processes of gaseous and particulate air pollution over the Mediterranean Basin (MB). Firstly, we investiga- ted the evolution of surface ozone (O3) over the MB over the time period 2000-2100 in a context of climate change, using the Atmospheric Chemistry and Climate Model In- tercomparison Project (ACCMIP) outputs from 13 models. Compared to the reference period (2000), we found a net decrease in the ensemble mean surface O3 over the MB in 2030 (2100) for 3 RCPs (Representative Concentration Pathway) : -14% (-38%) for RCP2.6, -9% (-24%) for RCP4.5 and -10% (-29%) for RCP6.0. For the RCP8.5 scenario, the ensemble mean surface O3 is almost constant over the MB from 2000 to 2100. Se- condly, we identified the geographical sources and the transport pathways of polluted air masses inducing high levels of surface O3 and carbon monoxide (CO) concentrations in di erent regions of the MB, representative of the west, the center and the east of the MB between 2012 and 2014, using several backward trajectory statistical analyses combining in situ measurements and back trajectories obtained from the HYSPLIT (HYbrid Single- Particle Lagrangian Integrated Trajectory) model. In general, O3 and CO are transported to the MB from continental Europe and Eastern Europe, respectively. Finally, we studied the import and export processes of pollution over the MB using the chemical transport model MOCAGE (MOdele de Chimie Atmosphérique à Grande Échelle) and the HYS- PLIT model. We also investigated in situ measurements carried out during both TRAQA (TRAnsport à longue distance et Qualité de l'Air) (2012) and GLAM (Gradient in Longi- tude of Atmospheric constituents above the Mediterranean basin) (2014) field campaigns performed within the framework of the ChArMEx (The Chemistry-Aerosol Mediterranean Experiment) program. We highlighted the long-range transport of air masses rich in O3 and the impact of the Mistral wind on the air mass mixing. The budget of O3 and CO was also performed over the MB for the year 2012 using the MOCAGE model simulations. We found that the MB is an import area for CO during the spring-summer period, whilst tropospheric O3 is imported to the MB during the January-June period and exported the rest of the year.

The Community Earth System Model (CESM) is a coupling of five different models which are combined to simulate the dynamic interactions between and within the Earth's atmosphere, ocean, land, land-ice, and sea-ice. In this work, the installation and testing of CESM on Portland State University's Cluster for Climate Change and Aerosol Research (CsAR) is described and documented, and two research applications of the model are performed. First, the improved treatment of cloud microphysics within recent versions of CESM's atmospheric module is applied to an examination of changes in shortwave cloud forcing (SWCF) and results are compared to output from older versions of the model. Second, the CESM model is applied to an examination of the effect that increased methane (CH4) concentrations have had on the catalytic destruction of stratospheric ozone (O3) by ozone depleting compounds (ODCs) such as chlorofluorocarbons (CFCs) and nitrous oxide (N2O).

Microbubbles are small gas-filled bubbles with diameters ranging from 50 to 1 μm, and less than 200 nm are called nanobubbles. Their small sizes and large specific surface area result in a high gas dissolution rate and long lifetime in liquid. Ozone is a strong oxidant that destroys microorganisms and only produces oxygen as the final by-product in fresh water. However, due to the poor stability of aqueous ozone, critical gas waste happens during treatments which leads to a high economic loss. Microbubbles have shown promising enhancement of ozone treatment. In previous studies, ozone microbubbles exhibited excellent efficacy in the removal of organic contaminants and inactivation of microorganisms including bacteria, spores, and fungi, but few articles discuss the virus inactivation of ozone microbubbles treatment. Human noroviruses (NoVs) are the primary cause of foodborne illnesses in the US, and the development of effective inactivation methods is crucial. Because of the absence of suitable in vitro cultivation methods for NoVs and the constraints of the available infectivity models for these viruses, most of the studies about inactivation use surrogate viruses that are similar to NoVs in genetics and structure. Tulane virus is a NoV surrogate that can identify the same putative co-factor. This study focuses on the influence of treatment time, disinfectant air exposure, and the presence of organic contaminants on the inactivation efficacy of ozone microbubbles or millimeter bubbles. The results demonstrate that more than one log10 reduction was produced when the Tulane virus was exposed to ozone millimeter bubbles and ozone microbubbles for a short period of time, even in the presence of high organic load (FBS), and the protective effect of the organic load was shown when the disinfectant induced volume increased. The findings indicate that conducting further research on ozone microbubbles in aqueous applications in food-related applications is useful.

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No / Originally developed as a heat exchange fluid, Volasil 245 (decamethylcyclopentasiloxane) has been found to dissolve 10 times more ozone than water does. This article proposes and investigates the extraction of wastewater contaminants to ozone-loaded Volasil 245 as a means of providing rapid treatment. In a series of bench-scale tests, the effectiveness of ozone-loaded Volasil 245 contact was compared with that of conventional gas contact. Tests were conducted with respect to a range of organic compounds: namely, phenol, 2-chlorophenol, 2,3-dichlorophenol, 1,3-dichlorobenzene, o-nitrotoluene, and nitrobenzene. Contact with the ozone-loaded solvent was suggested to be the more rapid technique, reducing aqueous concentrations by at least 85% within 30 s. In the case of 2-chlorophenol, Volasil 245 contact was shown to require just ~0.5 min to achieve a residual aqueous fraction of 5%, as opposed to ~4.5 min of gas contact. However, water/solvent interfacial mass transfer resistance was suggested to limit the degree of aqueous decontamination ultimately achieved.

Radish plants (Raphanus sativus L. cv Cherry Belle) were exposed to 0.10 μl l⁻¹ ozone (O₃) or 0.50 μl l⁻¹ sulfur dioxide (SO2) for 4 h d⁻¹, 3 d wk⁻¹ for 3 weeks. From these fumigated plants, individuals were selected that were resistant or sensitive to these pollutants. The selected plants were used as parental material in a breeding program to produce lines differing in resistance to O₃ and SO₂. Non-selected (NS) plants from the original populations served as controls. F₁ populations were raised and exposed to O₃ or SO₂ with the same fumigation regime used for the parents. The plants were harvested 30 days after emergence and dry weights were determined. Plants selected for O₃ resistance (O3R) weighed significantly more than either plants selected for sensitivity to O₃ (O₃S) or NS plants when exposed to either O₃ or SO₂. The hypocotyl was most affected by pollutant exposure, leading to reduced root/shoot ratios. Plants selected for resistance or sensitivity to SO₂ generally had biomass production similar to that of NS plants. Growth analysis at early stages of growth indicated that both O₃R and O₃S plants had less growth under O₃ fumigated conditions; however, by maturity O₃R plants had similar amounts of growth under fumigated or non-fumigated conditions. Ozone fumigations tended to decrease free sugar concentrations in leaves at early stages of growth in both O₃R and O₃S plants, and caused some accumulations of carbohydrates during late stages of growth in O₃S plants. Allocation of Mc was significantly lower to hypocotyls and roots of O₃ fumigated O₃S plants. Allocation to hypocotyls of O₃R plants was not affected, although both O₃R and O₃S plant groups had lower photosynthetic rates due to O₃ fumigation. Ozone did not significantly affect chlorophyll concentrations in leaves of either sensitive or resistant plants, nor was the time of new leaf production affected by fumigation. These experiments demonstrated the potential of O₃ to influence the composition of sensitive plant populations. However, SO₂ was a much less powerful influence on the composition of these populations. / Ph. D.

No description available.

Resumé: Protection of the ozone layer of the Earth from the perspective of law This thesis is dealing with protection of the ozone layer. I chose this topic because I consider ozone layer as a very important folder of the environment and its weakening is of global nature and for its protection it was necessary to involve as many countries as possible. This work is focused mainly on the development of ozone layer protection at the international level and on current legislativ. It also includes the European Union's approach to this problem. In the beginning of my thesis I'm trying to explain what is ozone, which substances deplete the ozone layer and which principles and tools are used for its protection. Chapter two is dedicated to the development of ozone layer protection. It includes the beginnings of the international cooperation which began to take shape in the middle of the 70s when was published the first scientific work, which pointed to damage of ozone layer by halogenated hydrocarbons. International cooperation resulted to the adoption of the Vienna Convention for the Protection of the Ozone Layer and later to its implementation protocol - Montreal protocol, in September of 1987. The Montreal Protocol was considered an exceptional success of diplomacy in the sphere of environmental protection but in...