Neste trabalho buscaram-se formas de aumentar a eficiência do processo de ozonização sobre a degradação/mineralização de corantes empregados pela indústria têxtil, especificamente do azocorante Preto Remazol B, avaliando o emprego do processo de ozonização catalítica tanto homogênea quanto heterogênea. O ozônio mostrou uma grande eficiência para promover a degradação dos três tipos de corantes estudados (azo, antraquinona e ftalocianina); permitindo que soluções destes corantes com concentração de 100 mg L-1 sofressem uma total descoloração (destruição do grupo cromóforo) em menos de 2 minutos de ozonização. Em meio ácido, o ozônio tende a reagir via o mecanismo direto e devido a isto a redução no teor de carbono orgânico total (COT) dos poluentes costuma ser menos eficiente. Em 30 minutos de tratamento o processo O3/pH3 permitiu somente 30% de mineralização do azocorante estudado. Por outro lado, o O3 pode ter sua decomposição catalisada por vários materiais, levando à formação de espécies radicalares, principalmente o radical hidroxila (HO.). Devido ao caráter não seletivo dos radicais hidroxila, o mecanismo de ozonização indireto costuma ser mais eficiente na oxidação de compostos orgânicos. Um exemplo clássico deste mecanismo é o processo O3/pH11, que mineralizou 56% do COT do azocorante após 30 minutos de ozonização. Uma estratégia para promover uma melhora na mineralização do corante Preto Remazol B pelo processo de ozonização em meio ácido foi a adição de peróxido de hidrogênio ao meio reacional. O tratamento O3/pH3/H2O2 permitiu um aumento de 51% na mineralização do azocorante após 30 minutos de ozonização. O aumento da eficiência do ozônio também foi avaliado empregando-se o processo de ozonização na presença de metais (Mn2+e Fe3+). Em 30 minutos de tratamento, o processo O3/pH3/Mn2+ mineralizou 67, 78 e 57% do COT dos corantes Preto Remazol B, Azul Brilhante RN e Turquesa Remazol G, respectivamente. No mesmo tempo de tratamento O3/pH3/Fe3+ permitiu uma remoção de COT de 57, 64 e 41% para Preto Remazol B, Azul Brilhante RN e Turquesa Remazol G, respectivamente. A presença dos metais estudados na forma sólida (MnO2) ou em suportes (SiO2/MnO2 e SiO2/Fe2O3), além de permitir uma remoção de até 79% do COT do azocorante em 30 minutos de tratamento, também mostra uma alternativa para viabilizar o emprego dos agentes catalisadores da decomposição do ozônio, uma vez que na forma suportada os mesmos podem ser utilizados de forma contínua, minimizando etapas de recuperação ou perdas destes materiais. / The main goal of this study was to find means to increase the efficiency of ozonation process over the degradation/mineralization of dyes used in the textile industry, mainly the azodye Remazol Black B, evaluating the use of either homogeneous or heterogeneous catalytic ozonation methods. Ozone showed great efficiency to promote the degradation of the three types of studied dyes (azo, anthraquinone and phtalocyanine) enabling the discoloration (destruction of chromophore group) of solutions with 100 mgdye L-1 in less than 2 minutes. In acidic medium, ozone tends to react via the direct mechanism. In this way, the reduction of total organic carbon (TOC) of the polluents uses to be less efficient. In 30 minutes of treatment, the process O3/pH3 allowed only 30% of mineralization of the studied azodye. On the other hand, O3 can be decomposed by several materials, leading to the formation of radical species, mainly the hydroxyl radical (HO.). Due to the nonselective character of hydroxyl radicals, the indirect mechanism of ozonation usually is more efficient in the oxidation of organic compounds. A classic example of this mechanism is the process O3/pH11 that mineralized 56% of TOC of the azodye after 30 minutes of ozonation. Another strategy to promote an improvement in the mineralization of the azodye Remazol Black B using the ozonation process in acid medium was the addition of hydrogen peroxide to the reactional medium. The treatment O3/pH3/H2O2 enabled an increase of 51% in the mineralization of the azodye after 30 minutes. The increase in the efficiency of ozone was also evaluated using the ozonation process in the presence of metallic ions (Mn2+ and Fe3+). In 30 minutes of treatment, the process O3/pH3/Mn2+ mineralized 67, 78 and 57% of the TOC of the dyes Remazol Black B, Blue Brilliant RN and Remazol Turquoise G133, respectively. In the same time of treatment, the process O3/pH3/Fe3+ mineralized 57, 64 and 41% of the TOC of he dyes Remazol Black B, Blue Brilliant RN and Remazol Turquoise G133, respectively. The presence of the studied metals in the solid form (MnO2) or on supports (SiO2/MnO2 e SiO2/Fe2O3), enabled the removal of up to 79% of the TOC of the azo in 30 minutes of ozonation. Moreover, these methods showed an alternative to permit the use of catalytic agents to decompose ozone, as in the supported form, they can be used in a continuous form, minimizing steps of recuperation or loss of these materials.

L'anomalie isotopique de l'ozone observée au début des années 1980 a été la première manifestation de fractionnement isotopique indépendant de la masse d'origine chimique. Attribuée au départ, essentiellement au processus de formation de l'ozone, les travaux récents mettent en évidence d'autres contributions telles que la photodissociation. Cette thèse utilise une approche théorique basée sur des calculs ab initio de chimie et dynamique quantique pour déterminer les sections efficaces d'absorption et leurs variations isotopiques. Ces sections efficaces permettent d'étudier la photodissociation de l'ozone par irradiation du soleil (flux actinique) ; ce qui permet une évaluation précise du processus de photodissociation à l'enrichissement isotopique de l'ozone. Ces résultats pourront être intégrés dans un modèle global prenant en compte à la fois les processus de formation et de destruction de l'ozone. / The ozone isotopic anomaly observed in early 1980s has been the first occurance of mass independent fractionation of chemical origin. Assigned first, essentially to the ozone formation process, recent works show additional contributions such as the photolysis process. This thesis uses a theoretical approach based on ab initio quantum chemistry and dynamics computations to obtain the absorption cross sections and their isotopic variations. The absorption cross sections allow to study ozone's photodissociation by solar irradiation (actinic flux) ; which enables an accurate evaluation of the photodissociation process in ozone's isotopic enrichment. Obtained results could be integrated in a global model that takes into account both ozone's formation and destruction processes.

<p>Several physical mechanisms concerning the impact of Rossby waves on ozone distribution and circulation in the stratosphere and troposphere are studied in the thesis.</p><p>Summertime total ozone variability over Middle Asia and Northern Scandinavia shows similar wave-like behaviour with typical periods of 10-20 days and amplitudes of 20-50 Dobson units. These variations are caused by eastward travelling Rossby waves in the lower stratosphere. The same mechanism plays the primary role in the formation of an intense low ozone episode over Scandinavia in August 2003. A strong anticyclone was formed in the troposphere over Europe as a part of a Rossby wave train. The anticyclone coincides with a displaced Artic pool of low-ozone air in the stratosphere aloft of the anticyclone. A combination of the two above-mentioned processes results in the total ozone minimum over Northern Europe for summer 2003.</p><p>Interannual variability of the atmospheric circulation and total ozone during winter is strongly controlled by the diabatic (Brewer-Dobson) circulation which is driven by upward propagating waves from the troposphere. In the Northern Hemisphere midlatitudes, wintertime total ozone shows antiphase behaviour with the Arctic Oscillation (AO) index on interannual and decadal time-scales. Weaker (stronger) wave activity leads to less (more) northward ozone transport and to a stronger (weaker) AO.</p><p>Rossby wave activity occurs as episodic wave events and this wave forcing is not uniform during winter. The November-December stratospheric eddy heat flux is strongly anticorrelated with the January-February eddy heat flux in the midlatitude stratosphere and troposphere. Weaker upward wave fluxes in early winter lead to stronger upward wave fluxes from the troposphere as well as to a stronger polar night jet during midwinter and vice versa. Hence upward wave activity fluxes in early winter define, to a considerable extent, the subsequent evolution of the midwinter circulation in the stratosphere and troposphere.</p>

Several physical mechanisms concerning the impact of Rossby waves on ozone distribution and circulation in the stratosphere and troposphere are studied in the thesis. Summertime total ozone variability over Middle Asia and Northern Scandinavia shows similar wave-like behaviour with typical periods of 10-20 days and amplitudes of 20-50 Dobson units. These variations are caused by eastward travelling Rossby waves in the lower stratosphere. The same mechanism plays the primary role in the formation of an intense low ozone episode over Scandinavia in August 2003. A strong anticyclone was formed in the troposphere over Europe as a part of a Rossby wave train. The anticyclone coincides with a displaced Artic pool of low-ozone air in the stratosphere aloft of the anticyclone. A combination of the two above-mentioned processes results in the total ozone minimum over Northern Europe for summer 2003. Interannual variability of the atmospheric circulation and total ozone during winter is strongly controlled by the diabatic (Brewer-Dobson) circulation which is driven by upward propagating waves from the troposphere. In the Northern Hemisphere midlatitudes, wintertime total ozone shows antiphase behaviour with the Arctic Oscillation (AO) index on interannual and decadal time-scales. Weaker (stronger) wave activity leads to less (more) northward ozone transport and to a stronger (weaker) AO. Rossby wave activity occurs as episodic wave events and this wave forcing is not uniform during winter. The November-December stratospheric eddy heat flux is strongly anticorrelated with the January-February eddy heat flux in the midlatitude stratosphere and troposphere. Weaker upward wave fluxes in early winter lead to stronger upward wave fluxes from the troposphere as well as to a stronger polar night jet during midwinter and vice versa. Hence upward wave activity fluxes in early winter define, to a considerable extent, the subsequent evolution of the midwinter circulation in the stratosphere and troposphere.

The purpose of this study was to investigate preservice science teachers&rsquo / mental models about the role and distribution of ozone layer and ozone layer depletion regarding their ontological orientation. This study was conducted with twenty four preservice science teachers who were enrolled in Elementary Science Education Program of Education Faculty of one public university located in Central Anatolia. From each grade level six preservice science teachers were selected / two from low achiever, two from middle achiever and two from high achiever. Moreover, in the study, data were collected by using semi structured interview and interview consists of eleven questions and with five questions having multiple parts. Interview recordings were transcribed and analyzed qualitatively. In the following steps of the analysis, researcher proceeded with the already formed and described codes in an easygoing way. The results revealed that preservice science teachers&rsquo / responses were mostly seen as skin cancer and sunburn as harmful effects of ultraviolet rays and preservice science teachers&rsquo / responses were mostly seen as activation vitamin D and photosynthesis of plants as beneficial effects of Sun&rsquo / s rays. Half of preservice science teachers thought that ozone layer exists in the atmosphere. Moreover, preservice science teachers&rsquo / responses were mostly seen as perfume, deodorant, car, and spray as harmful materials to ozone layer. Chlorofluorocarbon, carbon monoxide, and carbon-dioxide were the most seen responses as harmful chemicals to ozone layer. Similar misconceptions were identified when compared with past studies. Also, different misconceptions were found in the study. Ten distinct models were formed regarding role and distribution of ozone layer and five distinct models were formed regarding ozone layer depletion. Moreover, absorbing and reflecting surface was mostly seen ontological belief regarding role and distribution of ozone layer. Hole was mostly seen ontological belief regarding ozone layer depletion. Generally, achievement and grade level did not make difference among preservice science teachers forming which type of mental models and having ontological beliefs.

In the U.S. and other developed countries, humans spend the vast majority of their time within the built environment. As a result, a substantial portion of our collective exposure to airborne pollutants, even those of outdoor origin, occurs in indoor environments. In addition, building construction materials and operational practices are changing as we endeavor to reduce the energy burden of the built environment. These changes result in barriers and opportunities in mitigating exposure to indoor pollutants and the accompanying implications for human health. This dissertation advances knowledge regarding low-energy control of indoor ozone. Ozone is often considered a pollutant of outdoor concern. However, ozone in indoor environments presents important challenges regarding exposure, intake, and chemistry in the built environment. The investigations in this dissertation extend the state understanding of indoor transport and transformation of ozone, and the potential for using material-surface interactions in buildings to suppress concentrations of indoor ozone. The first objective relates to the determination of magnitudes of ozone removal and product emissions at room or building scales. This objective provides new data on reactive uptake and product generation in large-scale environments, develops Monte Carlo models describing indoor ozone removal by materials in homes, and compares active and passive methods of indoor ozone removal. The second objective addresses the need to develop improved air cleaning materials through experiments and modeling that address material-ozone reactions in porous materials. This objective advances the state of modeling heterogeneous reactive uptake of ozone by characterizing material physical properties and transport phenomena, determining their impact on ozone removal, and using these data to develop a more mechanistic model of material-ozone reactions. Ultimately, these investigations advance the engineering concepts that support the development of passive indoor pollutant controls, an important tool for reducing concentrations of indoor pollutants while supporting low-energy building initiatives. The combination of experimental characterization of ozone deposition velocities and product emission rates, whole-building Monte Carlo modeling, and mechanistic material/pollutant models provide important new data and approaches that expand the state of knowledge of the fate and transport of reactive pollutants in indoor environments. / text

Η παρούσα διπλωματική εργασία πραγματεύεται την χρήση τεχνητών νευρωνικών δικτύων για την δημιουργία ενός αξιόπιστου μοντέλου πρόβλεψης της μέγιστης ημερήσιας συγκέντρωσης του τροποσφαιρικού όζοντος σε αστικό περιβάλλον. Η ανάλυση και η πρόβλεψη των επιπέδων της ατμοσφαιρικής ρύπανσης, είναι σημαντικά θέματα της ατμοσφαιρικής και περιβαλλοντικής έρευνας, λόγω του αντίκτυπου που έχει η ατμοσφαιρική ρύπανση στην υγεία και την ποιότητα ζωής του ανθρώπου. Ένας από τους πιο σημαντικούς ρύπους είναι το τροποσφαιρικό όζον (O3), και ειδικότερα το όζον του κατώτερου οριακού στρώματος της ατμόσφαιρας (επιφανειακό ή surface ozone). Επομένως, η πρόβλεψη της μέγιστης συγκέντρωσης όζοντος στις πυκνοκατοικημένες αστικές περιοχές, είναι μεγάλης σπουδαιότητας για τον έλεγχο και τη βελτίωση της ποιότητας της ατμόσφαιρας. Μέχρι σήμερα, αν και διάφορα μοντέλα πρόβλεψης όζοντος έχουν ερευνηθεί, υπάρχει ακόμα η ανάγκη για ακριβέστερα μοντέλα, έτσι ώστε να αναπτυχθούν αποτελεσματικές στρατηγικές πρόληψης και ελέγχου σε περιπτώσεις που οι οριακές τιμές όζοντος ξεπερνιούνται πέρα από κάποιο συγκεκριμένο χρονικό διάστημα (επεισόδιο ρύπανσης). Χρησιμοποιήθηκαν χρονοσειρές συγκέντρωσης όζοντος και άλλων ρύπων που οδηγούν στην δημιουργία του, από το σταθμό της “Λυκόβρυσης” και του “Αμαρουσίου”, καθώς και μετεωρολογικά δεδομένα που σχετίζονται με την δημιουργία, καταστροφή και διασπορά ή διάχυση του όζοντος. Κατά τη βελτιστοποίηση του νευρωνικού δικτύου, δόθηκε έμφαση στην κατά το δυνατόν ακριβέστερη πρόγνωση των αυξημένων τιμών της συγκέντρωσης Ο3 (επεισόδια ρύπανσης για [Ο3] >=180 μg/m3), για τις οποίες απαιτείται η λήψη εκτάκτων μέτρων. Τα Τεχνητά Νευρωνικά Δίκτυα, όπως αποδείχθηκε, αποτελούν μια πολύ καλή εναλλακτική λύση ως προς τις παραδοσιακές στατιστικές τεχνικές, καθώς για την εκπαίδευσή τους χρησιμοποιούνται διαθέσιμα στοιχεία προηγούμενων μετρήσεων αλλά και λόγω της ικανότητάς τους να χειρίζονται δεδομένα με μη γραμμικές σχέσεις μεταξύ τους. Αρχικά δοκιμάστηκαν διαφορετικές αρχιτεκτονικές νευρωνικών δικτύων επιτρέπουν την κατηγοριοποίηση των πρότυπων δεδομένων εισόδου, όπως οι χάρτες Kohonen, τα δίκτυα επιβλεπόμενης κατηγοριοποίησης LVQ και τα στοχαστικά RBF δίκτυα με σκοπό το μοίρασμα των δεδομένων εισόδου σε κατηγορίες σύμφωνα με τα επίπεδα όζοντος. Στη συνέχεια ελέγχθηκε η δυνατότητα πρόβλεψης με την χρήση πολυστρωματικών αντιληπτήρων πρόσθιας τροφοδότησης (Multilayer Feed-Forward) και εποπτευόμενης μάθησης μέσω διόρθωσης σφάλματος με ανατροφοδότηση (Back Propagation), γνωστά ως ΜultiLayer Perceptrons ή MLPs που έδωσαν και τα καλύτερα αποτελέσματα. Η απόδοση ενός μοντέλου πρόβλεψης της συγκέντρωσης του όζοντος της χαμηλής τροπόσφαιρας μπορεί να κριθεί από το ποσοστό των επεισοδίων που θα προβλεφθούν σωστά από το μοντέλο, σε αντιδιαστολή με το ποσοστό των ψεύτικων-λανθασμένων συναγερμών (δηλ. προβλέψεις επεισοδίων ρύπανσης που δεν συνέβησαν στην πραγματικότητα). Ο δείκτης απόδοσης SI, είναι ο δείκτης υψηλότερης σπουδαιότητας καθώς αντιπροσωπεύσει την απόδοση στην πρόβλεψη των επεισοδίων αλλά και στην γενικότερη συμφωνία μεταξύ των προβλεφθέντων και παρατηρηθέντων δεδομένων. Στο σταθμό της “Λυκόβρυσης” ο δείκτης απόδοσης SI κυμάνθηκε από 0,943 έως 0,831 και ο λόγος των ψεύτικων συναγερμών FA από 0 έως 0,014 ενώ στο σταθμό του “Αμαρουσίου” ο δείκτης απόδοσης SI κυμάνθηκε από 0,777 έως 0,68 και ο λόγος των ψεύτικων συναγερμών FA από 0,211 έως 0,234. / This study deals with the use of artificial neural networks for ground-level ozone modeling in the Athens area. Forecasting next day’s maximum hourly ozone concentration is an important topic of air quality research nowadays. The continuing worldwide environmental problem suggests the need for more accurate forecasting models. Development of such models is a difficult task as the meteorological variables and the photochemical reactions involved in ozone formation are complex. Meteorological variables and concentrations of ozone and ozone precursors, from two monitoring stations “Lykovrisi” and “Marousi”, are used as inputs in order to obtain the best estimate of the next day’s maximum hourly ozone concentration. The violation of the European public information threshold (ozone episode), defined by control authorities, of 180 μg/m3 is successfully predicted in most cases. Neural networks seem to be very well situated since they allow for nonlinear relations among input variables. Several architectures of Neural Networks were tested but Multi-Layer Perceptrons (MLPs) came up with the best results. At “Lykovrisi” monitoring station the Success Index (SI) that is able to represent performance in forecasting exceedances as well as the overall goodness between predicted and measured data, varied from 0.943 to 0.831 and the fraction of False Alarms (FA) that represents predicted episodes that didn’t happen to the overall number of predicted episodes, varied from 0 to 0.014. At “Marousi” monitoring station the SI varied from 0.777 to 0.68 and the fraction of False Alarms (FA) from 0.211 to 0.234.

Surface ozone (O3) is one of the most toxic and abundant air pollutants. It has deleterious effects on human and animal respiration processes, and adversely affects plants. Four sites were selected for monitoring ambient O3 in the Durban metropolitan area: Botanic Gardens, University of Natal (UND), top of Kloof Gorge, and Mooi River. At each site tobacco Bel-W3 bioindicators, and NO2 and O3 passive diffusion tubes were placed. An O3 analyser (Dasibi 1108) was situated at the UND site. Monitoring was carried out for four weeks during summer, autumn and winter at each site, and during spring at the UND site. Two weeks of data from the diffusion tubes were collected during spring, from the Nelspruit area, Mpumalanga. Ozone concentrations measured with the Dasibi at the UND site were low in comparison to other urban-industrial areas in the world, with hourly values falling between 5ppb and 10 ppb. The highest hourly mean maximum recorded was 40ppb. A general spring/winter maximum and summer minimum was observed. This is typical of subtropical locations, where subsidence in prevailing anticyclonic circulation occurs. Diurnal characteristics included early morning minima and maxima at 12h00 in spring and summer, and maxima approximately two hours later in autumn and winter. This pattern was typical of that found in polluted environments, the magnitude, however, being lower. An unusual secondary nocturnal peak occurred during autumn, winter and spring. This could have been due to the long-range transport of relatively O3-rich air from a non-urban, high altitude inland area. Ozone concentrations were not strongly influenced by meteorological variables. Diffusion tube data indicated low O3, however, the coefficients of variation were high, implying a lack of precision in this technique. This technique would have to be improved before data obtained could be regarded as valid. Nitrogen dioxide, NO2, one of the precursors to O3, was monitored using diffusion tubes at the same sites. Concentrations were highest closer to the city centre, the highest concentration being 31ppb in autumn. In the Mpumalanga study, NO2 concentrations were higher in the city of Nelspruit than the surrounding areas. No significant differences were found in the O3 concentrations between the Mpumalanga sites. The tobacco plants showed the highest visible leaf injury in winter, corresponding with the higher Dasibi values, but there were no significant differences between the sites, and no significant differences in chlorophyll contents between the sites. In this study, O3-induced injury occurred below the previously established threshold of 40ppb. / Thesis (M.Sc.)-University of Natal, Durban, 1998.

La dégradation catalytique du PMMA a été réalisée avec succès à des températures inférieures à 300°C. L’utilisation de zéolithe comme catalyseur a permis de réduire la température de réaction par rapport aux procédés classiques de dégradation thermique. On a montré que la distribution des produits de réaction obtenus en réacteur discontinu dépend des propriétés acides du catalyseur, tandis que la composition de la fraction liquide est directement liée à la sélectivité de forme du catalyseur. Un procédé continu à lit fixe a été développé qui a permis d’obtenir le monomère MMA comme produit principal. L’augmentation de la température de réaction de 200 à 270°C a montré un effet positif sur le rendement en produit liquide. Cependant, des températures de réaction supérieures ont favorisé le craquage du monomère en produits gazeux. Une désactivation significative de la zéolithe ZSM-5 a été observée après 120 heures d’opération, entraînant une diminution du rendement en produit liquide. La régénération des extrudés de ZSM-5 cokés a pu être réalisée par ozonation à basse température - inférieure à 150°C. On a étudié les effets de la température, du débit de gaz et de la concentration en ozone sur l’élimination de carbone. Le décokage par l’ozone a débuté dès 50°C et montré un optimum à 100°C (avec une conversion de 80%). Des températures plus élevées ne se sont pas avérées bénéfiques, en raison de la forte limitation de la diffusion interne de l’ozone qui confine en surface la production de radicaux et donc le processus de régénération. Dans les conditions optimales, l’ozonation a presque complètement restauré l’activité de la zéolithe sans en endommager la texture et les sites actifs, comme le montrent les résultats de craquage du PMMA obtenus avec le catalyseur ainsi régénéré. / Catalytic degradation of PMMA was successfully performed at temperatures below 300°C. The use of zeolite catalyst could reduce reaction temperature in comparison with an ordinary thermal degradation process. It was found that the product distribution obtained from batch experiment depends on zeolite acid properties whereas the composition of the liquid fraction is directly related to the shape selectivity of the catalyst. A continuous fixed bed process was designed that allowed to obtain MMA monomer as main product. The increase of reaction temperature from 200 to 270°C showed a positive effect on the liquid product yield. However, at higher temperatures, the light product was further cracked into gaseous products. Significant deactivation of ZSM-5 catalyst was observed after 120 hours of operation, resulting in a decrease in liquid product yield. Regeneration of the coked ZSM-5 extrudates was achieved by oxidation with ozone at low temperatures, below 150°C. The effects of temperature, GHSV and inlet concentration of ozone on carbon removal efficiency were studied. Carbon removal with ozone started at 50°C and reached a maximum of 80% at 100°C. Higher temperatures were not beneficial due to the strong limitation of ozone diffusion which confines radical production then the regeneration process to the outer surface. In optimal conditions, ozonation almost fully restored the zeolite activity without damaging the texture and active sites of zeolite, as shown from the results of regenerated catalyst in PMMA cracking

Le manque de compréhension des réactions liées à l'utilisation de l'ozone a constitué un clair frein au développement de séquences de blanchiment non-chlorées efficaces. Considéré comme un élément central des séquences TCF face aux séquences ECF comprenant du dioxyde de chlore, l'ozone ne permettait pas l'obtention de pâtes cellulosiques de qualité aussi élevée. Le but de ce travail est l'élaboration de séquences de blanchiment non-chlorées permettant l'obtention d'un produit final de haute qualité. Ce type de séquence pourrait présenter de nombreux avantages, parmi lesquels sont envisagés des gains environnementaux indéniables. Afin d'atteindre cet objectif, les réactions liées à l'ozone et au peroxyde d'hydrogène ont été étudiées plus avant. Après une revue bibliographique, cet écrit revient dans un second chapitre sur certaines hypothèses de la littérature qui, confrontées entre elles et avec certains premiers résultats, permettent de mettre en évidence certaines incohérences. Dans une troisième partie, plusieurs pâtes de compositions différentes ont été étudiées, afin de vérifier l'ordre des réactions de l'ozone sur les divers composés d'une pâte kraft, et afin également d'envisager l'ampleur des dégradations subies par la cellulose dans ces différents substrats, qu'il s'agisse de dépolymérisation, ou de modifications fonctionnelles. Ces résultats ont permis de formuler une hypothèse relative aux réactions de l'ozone sur des composés insaturés, tels que ceux des acides hexenuroniques. Par l'utilisation d'une méthode de détection rarement utilisée en papeterie, cette hypothèse a été validée : la réaction de l'ozone sur certains composés insaturés non-aromatiques pourrait générer des radicaux, eux-mêmes à l'origine de mécanismes de modification de la cellulose. D'après les résultats, l'ozone ne serait que marginalement directement responsable des dégradations de la cellulose. L'effet des différents stades alcalin a également été envisagé dans une quatrième partie. C'est ainsi que la dépolymérisation de la cellulose et ses modifications fonctionnelles ont également été analysées à l'issue de ces stades. Les résultats suggèrent notamment l'existence d'un mécanisme de dépolymérisation impliquant les carbonyles cellulosiques et des agents nucléophiles. Une grande partie de la dégradation se produisant dans les stades au peroxyde d'hydrogène lui serait ainsi imputable. Le dernier chapitre revient sur ces différentes considérations, dans l'optique de minimiser les inconvénients liés à ces différents stades, et particulièrement aux stades à l'ozone. Différentes combinaisons des réactifs ont été envisagées pour former des séquences non-chlorées. Les résultats montrent que l'obtention de pâtes de qualité comparable à celle de pâtes issues de séquences de blanchiment chlorées est possible. / The lack of understanding regarding the reactions of ozone with pulp components is one of the reasons why chlorine-free bleaching never really developed. Ozone is actually believed to lead to an extensive degradation of cellulose, contrary to the agent it could replace: chlorine dioxide. However, as the use of chlorinated compounds has many drawbacks, including the generation of toxic compounds, non-degrading chlorine-free bleaching sequences have to be designed. To do so, a better understanding of reactions involving ozone and hydrogen peroxide has to be gained. The first part of this very work consisted of a literature review. In the second part, some of the main hypotheses extracted from the literature were compared with other elements and first results, to show they inevitably led to contradictions and that new theories were needed. The third part was dedicated to ozone. The order of its reactions with pulp components was first of all checked. The properties of pulps of various compositions were then measured through ozonations. This study led to a new hypothesis, which was validated thanks to ESR spectroscopy. The reaction of ozone with some non-aromatic unsaturated compounds seems to give radical species. Those radical species would be in turn responsible for the depolymerization of cellulose, and the formation of carbonyl groups on cellulose as well. The fourth part dealt with the impact of alkaline treatment on cellulose after ozonations. Observations about carbonyl content and degree of polymerization suggest a new mechanism related to carbonyl and nucleophilic agents, explaining a main part of the depolymerization undergone by the cellulose. The last chapter of this work summarizes the trials regarding the optimisation of a chlorine-free bleaching sequence. It proves that high-quality pulps can be obtained by chlorine-free processes.