Η περιοχή μελέτης ανήκει στη ΒΔ Πελοπόννησο, εκτείνεται στο βόρειο τμήμα του νομού Ηλείας και στο νοτιοανατολικό τμήμα του νομού Αχαΐας, χαρακτηρίζεται από την εμφάνιση υπόθερμων θερμομεταλλικών πηγών, καταλαμβάνει έκταση περίπου 1500 Km2 και αναπτύσσεται σε διεύθυνση Α-Δ από τον Ερύμανθο ως τις δυτικές ακτές. Η περιοχή μελέτης οριοθετήθηκε με κύριο κριτήριο τη γεωλογική δομή και τη νεοτεκτονική εξέλιξη της ΒΔ Πελοποννήσου αλλά και τις υδρογεωλογικές συνθήκες, προκειμένου να ερευνηθεί η προέλευση της θερμομεταλλικής υδροφορίας της πηγής των Λουτρών Κυλλήνης καθώς και η σχέση της με τις υπόλοιπες θερμομεταλλικές εμφανίσεις της περιοχής μελέτης. Η αναζήτηση της ζώνης τροφοδοσίας της θερμομεταλλικής πηγής Κυλλήνης προέκυψε από την γεωλογική – υδρογεωλογική έρευνα στην περιοχή Λουτρών Κυλλήνης, σε συνδυασμό με τα στοιχεία υφιστάμενων μελετών, από όπου προκύπτει: 1) η σχέση του νερού της πηγής Κυλλήνης, μετεωρικής προέλευσης, με τους βαθύτερους υδροφορείς μέσω των ενεργών νεοδιαπειρικών ρηγμάτων, η δε ανάπτυξη της θερμομεταλλικής υδροφορίας εντοπίζεται σε μία ζώνη με γενική διεύθυνση Α-Δ, 2) η παροχή, η θερμοκρασία και η μεταλλικότητα της πηγής παρουσιάζει διαχρονικά σταθερότητα και το θερμό θειούχο νερό δημιουργείται εντός ασβεστολιθικών πετρωμάτων, που βρίσκονται σε μεγαλύτερες αποστάσεις σε σχέση με αυτά της περιοχής Κάστρου Κυλλήνης. Από τη γεωλογική, τεκτονική και υδρογεωλογική διερεύνηση της περιοχής μελέτης προκύπτει: 1) η δυνατότητα τόσο της κατακόρυφης όσο και της οριζόντιας σε βάθος κίνησης του νερού μέσω του σύνθετου τεκτονικού ιστού της περιοχής, 2) η από το κεντρικό τμήμα της μεταλπικής λεκάνης πιθανή επικοινωνία των θερμομεταλλικών νερών μέσα από τις ζώνες των ρηγμάτων της περιοχής και 3) η πιθανή τροφοδοσία αυτών από το καρστικό σύστημα των ανθρακικών σχηματισμών του Ερύμανθου. Από την υδροχημική – ισοτοπική έρευνα των νερών του δικτύου δειγματοληψίας που περιελάμβανε νερά πηγών και γεωτρήσεων τόσο γλυκού νερού όσο και θερμομεταλλικού, με διασπορά στην έκταση της περιοχής μελέτης, μελετήθηκε ο υδροχημικός χαρακτήρας των υπόγειων νερών και η ισοτοπική τους σύσταση. Συσχετίζοντας τις γεωλογικές – υδρογεωλογικές συνθήκες των εμφανίσεων της θερμομεταλλικής υδροφορίας στη περιοχή μελέτης με τα υδροχημικά τους χαρακτηριστικά (δηλαδή τους υδροχημικούς δείκτες, τη χημική ταξινόμηση, το χαρακτηρισμό του τύπου των νερών), σε συνάρτηση με την ισοτοπική τους σύσταση, επιβεβαιώνεται η κοινή προέλευση των γεωθερμικών ρευστών των διαφορετικών πηγών καθώς και η συμμετοχή του νερού των καρστικών υδροφορέων της ζώνης Πίνδου στη τροφοδοσία τους. Οι διαφορές που παρατηρούνται ωστόσο στη σύσταση στο σημείο εκροής (δηλαδή διαφορετική θερμοκρασία και αλατότητα, διαφορά στην παροχή, καθώς και μικρές διαφορές σε συγκεντρώσεις ιόντων), μαρτυρούν τη διαφορετική πορεία του γεωθερμικού ρευστού από το γεωθερμικό ταμιευτήρα ως την επιφάνεια. / The region of study belongs to the SW Peloponnese, extends in the northern department of the province of Ilia and in the SE department of the province of Achaia, is characterized by the appearance of hypothermal geothermal-mineral springs, occupies extent approximately 1500 Km2 and is developed in direction E-W from Mount Erymanthos to the sea. The region of study was delimited with main criterion the geological structure and the neotectonic development of SW Peloponnese but also the hydrogeological circumstances so that the origin of the geothermal aquifer of the spring of Killini’s Baths as well as its relation with the remainder of the geothermal-mineral appearances in the region of study are searched. The inquiry of the recharge zone of the geothermal spring of Killini resulted from the geological – hydrogeological research in the region of Killini’s Baths in combination with the elements of pre-existing studies, from where it results: 1) the relation of the water in Killini’s spring, whose origin is meteoric, with the deeper aquifers via the active diapir faults as well as the growth of the geothermal aquifer which is located in an area with general direction Ε-W, 2) the supply, the temperature and the minerality of the spring present stability through the years and the hot, sulphurous water is created on the inside of limestone rocks, that are found in bigger distances in relation to those of the region of Killini’s Castle. From geological, tectonics and hydrogeological investigation in the region of study, it results: 1) the possibility of both vertical and horizontal in-depth water movement via the complex tectonic web of the region, 2) the likely communication of geothermal-mineral via the fault zones of the region in the central department of the post alpine basin 3) probable recharge of the geothermal-mineral from the karsts system of Mount Erymanthos carbonic formations. The hydrochemical character of the underground waters and their isotopic composition were studied, with dissemination in the extent of study region , by the hydrochemical-isotopic research of waters of network of sampling that included waters of springs and drillings both sweet and geothermal-mineral. The common origin of geothermal fluid coming from different springs as well as the participation of the karst aquifer of the zone of Mount Erymanthos in their recharge were confirmed by connecting the geological – hydrogeological conditions of the geothermal – mineral aquifer appearances in the region of study with their hydrochemical characteristics (hydrochemical indicators, the chemical classification, the characterization of water type) and in combination with their isotopic composition. However, the differences that are observed in the characteristics at the point of flow (different temperature and salinity, difference in the supply as well as small differences in concentration if ions), testify the different course of geothermal fluid from the geothermal basin to the surface.

Αντικείμενο της παρούσας διατριβής ήταν η μελέτη των δομικών και καταλυτικών ιδιοτήτων καταλυτών ΜοΟ3 υποστηριγμένων σε οξειδικούς φορείς. Η χρήση της φασματοσκοπικής μεθόδου Raman υπό ελεγχόμενες in situ συνθήκες επέτρεψε το χαρακτηρισμό των καταλυτών κάτω από ένα εύρος συνθηκών που μελετήθηκαν. Η εφαρμογή της μεθοδολογίας Operando Raman-GC οδήγησε σε συμπεράσματα αναφορικά με δομικές αλλαγές και δεδομένα καταλυτικής αποτελεσματικότητας ενώ συνδυασμός των δονητικών φασματοσκοπιών Raman και FTIR με πειράματα ισοτοπικής εναλλαγής 18Ο/16Ο χρησιμοποιήθηκε για εκτενέστερη διερεύνηση της μοριακής δομής των καταλυτών. Ειδικότερα εξετάσθηκε μια σειρά καταλυτών ΜοΟ3/ΤiO2 με in situ φασματοσκοπία Raman κάτω από οξειδωτικές και αναγωγικές συνθήκες, καθώς επίσης και κάτω από συνθήκες αντίδρασης οξειδωτικής αφυδρογόνωσης του αιθανίου. Η μοριακή δομή των επιφανειακών ειδών μολυβδενίου βρέθηκε να σχετίζεται άμεσα με το σχηματισμό κυρίως απομονωμένων ειδών Μο, για χαμηλές και υψηλές φορτίσεις κοντά στη μονοστρωματική κάλυψη, ενώ για φορτίσεις που υπερβαίνουν το μονόστρωμα παρατηρήθηκε ο σχηματισμός κρυσταλλικού ΜοΟ3. Η αποτίμηση της καταλυτικής ενεργότητας κατέδειξε πως καταλύτες με πολύ καλή διασπορά του ΜοΟ3 πάνω στην επιφάνεια παρουσιάζουν τα βέλτιστα αποτελέσματα. Επιπροσθέτως, εξετάζεται η επίδραση του φορέα (ZrO2, Al2O3, TiO2 και SiO2) στη δομή και στην καταλυτική συμπεριφορά μονοστρωματικών υποστηριγμένων καταλυτών MoO3 για την αντίδραση της οξειδωτικής αφυδρογόνωσης του αιθανίου με την φασματοσκοπία Raman. Μελετήθηκε η επίδραση της φόρτισης, της θερμοκρασίας, της σύστασης της αέριας τροφοδοσίας και του χρόνου παραμονής των αντιδρώντων πάνω στα χαρακτηριστικά των φασμάτων Raman καθώς και στην καταλυτική ενεργότητα με στόχο την εξαγωγή σχέσεων δομής-ενεργότητας/εκλεκτικότητας υποστηριγμένων καταλυτών MoO3/MxOy (M=Zr, Al, Ti, Si) για την οξειδωτική αφυδρογόνωση του αιθανίου. Η επιλογή της φύσης του φορέα/υποστρώματος κρίθηκε ως σημαντικός παράγοντας που ελέγχει την αποτελεσματικότητα της λειτουργίας των καταλυτών για την ODH του αιθανίου. Τέλος, οι δονητικές φασματοσκοπίες Raman και FTIR κάτω από ελεγχόμενες in situ συνθήκες χρησιμοποιήθηκαν για τη διερεύνηση της μοριακής δομής των καταλυτικών συστημάτων MoO3/ZrO2, MoO3/Al2O3 και MoO3/TiO2. Η φασματοσκοπία Raman σε συνδυασμό με πειράματα ισοτοπικής εναλλαγής 18Ο/16Ο οδήγησε σε αξιόλογα συμπεράσματα αναφορικά με τη μοριακή δομή των διεσπαρμένων μολυβδενικών ειδών υπό το πρίσμα της διάκρισης μεταξύ mono-oxo και di-oxo δομών. Τα αποτελέσματα συνέκλιναν στην παρουσία mono-oxo μοριακών διαμορφώσεων για κάθε καταλυτικό σύστημα (MoO3/ZrO2, MoO3/Al2O3 και MoO3/TiO2), τόσο για χαμηλές όσο και για φορτίσεις κοντά στο μονόστρωμα. Η υποκατάσταση γειτονικών οξειδικών θέσεων των Μο=16Ο δεσμών βρέθηκε να συμβάλει στη σταδιακή μετατόπιση της κορυφής αυτών των δεσμών σε χαμηλότερες συχνότητες μέσω ενός φαινομένου που ονομάστηκε “δονητικό ισοτοπικό φαινόμενο υποκατάστασης 18Ο/16Ο επόμενων κοντινότερων γειτόνων” (Next – Nearest – Neighbor 18Ο/16Ο substitution vibrational isotope effect). / The present work focuses on the study of structural and catalytic properties of the dispersed phase of supported MoO3 catalysts. In situ Raman spectroscopy has been used to characterize the supported catalysts and provide fundamental information about the configuration and the molecular structure under various controlled gas atmospheres and operating temperatures. A strategy involving the combined use of in situ Raman and in situ FTIR vibrational spectroscopies and the combined use of in situ Raman spectroscopy and 18O2/16O2 isotopic exchange experiments has been applied to investigate the molecular structure of the molybdena dispersed phase. A series of supported molybdenum oxide catalysts supported on TiO2(anatase) has been extensively examined by means of in situ and operando Raman spectroscopy under oxidizing, reducing and ODH of ethane conditions. The molecular structure of the surface MoOx species has been assigned to the formation of isolated units, primarily as O=Mo(–O–Ti)3 with a characteristic Mo=O sretching frequency observed at 994 cm-1 both at low as well as at high coverage below monolayer (~6 Mo/nm2). A weak and broad band at ~925 cm-1 due to Mo–O– Mo functionalities becomes visible with increasing loading, indicating a low presence of associated (polymeric) molybdates with increasing loading on TiO2. When exceeding monolayer coverage, the Raman spectra revealed the formation of bulk crystalline MoO3 on the TiO2 support. Detailed catalytic studies of the supported molybdena catalysts on titania showed that the monolayer catalyst (15MoTi) provide better catalytic results. Additionally, the structural and catalytic properties of monolayer MoO3 catalysts supported on ZrO2, Al2O3, TiO2 and SiO2 were studied for the oxidative dehydrogenation (ODH) of ethane by in situ and operando Raman spectroscopy. The molecular structure of the dispersed surface species evolves from isolated monomolybdates (MoO4 and MoO5) to associated (MoOx)n units in polymolybdate chains, depending on the support. The nature of the oxide support material and of the Mo–O–support bond has a significant influence on the catalytic behavior of the molybdena catalysts with monolayer coverage while, the dependence of reactivity on the support follows the order ZrO2 > Al2O3 > TiO2 > SiO2. The vibrational properties of molybdena catalysts supported on titania, zirconia and alumina were studied by means of in situ vibrational (Raman and FTIR) spectroscopies and 18O/16O isotopic exchange experiments combined with in situ Raman spectra at 450 °C. The aim of this work was the discrimination between mono-oxo and di-oxo configuration for the deposited molybdena phase at low as well as at high coverage near monolayer. The vibrational isotope effects and the combined interpretation of the observed Raman fundamental, IR overtone, as well as calculated zero-order band wavenumbers and characteristics suggest a mono-oxo configuration for the deposited molybdena phase at low as well as at higher coverage, irrespective of the extent of association (polymerization). A “nextnearest- neighbor 18O/16O substitution” vibrational effect is observed, resulting in small red shifts (2–7 cm−1) of the Mo=16O Raman band wavenumber. This effect is found to be strongly related to the nature of the support, regarding the extent of the shift, and assigned to the different reducibilities of the various support materials.

Made available in DSpace on 2014-10-09T12:28:35Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:56:02Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IEA/T / Universidade Karlsruhe, Alemanha

Les chaperonines sont des chaperonnes moléculaires indispensables pour le repliement de certaines protéines dans les cellules. La taille et la complexité de ces machineries biologiques rendent complexes l'étude de leurs propriétés structurales et fonctionnelles. La spectroscopie RMN permet de suivre des changements structuraux et dynamiques en temps réel avec une résolution atomique. Cependant, l'étude par RMN de protéines ou de complexes de haut poids moléculaires a été un challenge pendant de nombreuses années. Dans la première partie de cette thèse, il a été montré que la combinaison de marquage spécifique des groupements méthyles, d'expériences RMN optimisées et de microscopie électronique peut être utilisée pour suivre différents états du cycle fonctionnel d'une chaperonine de 1 MDa. Pour étudier ce mécanisme, la chaperonine native a été reconstituée avec un marquage des groupements méthyles des méthionines et valines. Les résidus méthionines ont pu être utilisés comme des sondes pour identifier les spectres RMN correspondant aux états intermédiaires et aux espèces actives du cycle fonctionnel. Grâce à ces sondes il a été possible de suivre en temps réel les réarrangements structuraux correspondant aux différentes conformations de la chaperonine durant son cycle fonctionnel. La seconde partie traite de la caractérisation de l'interaction de la chaperonine avec une protéine cliente dépliée. L'observation de la stabilisation de l'état déplié de la protéine par la chaperonine a permis de mettre en évidence une activité de "holdase" de la chaperonine. En utilisant une combinaison astucieuse de différents marquages de groupements méthyles et d'expériences RMN optimisés pour des assemblages de haut poids moléculaire, il a été possible d'observer le repliement de cette protéine par la chaperonine et les effets de la présence d'une protéine dépliée sur le cycle fonctionnel de la chaperonine en action. / Chaperonins are essential molecular chaperons for the refolding of proteins in the cells. Size and complexity of these biological machineries make complex the study of their structural and functional properties. NMR spectroscopy offers an unique ability to monitor structural and dynamic changes in real-time and at atomic resolution. However, the NMR studies of large proteins and complexes has been a real challenge for a long time. In the first part of this thesis, it has been shown that the combination of methyl specific labeling, optimized NMR spectroscopy for large assemblies and electron microscopy can be used to monitor the different states of the functional cycle of a 1 MDa chaperonin. To study this mechanism, the native chaperonin was reconstituted with a labeling of the methionines and valines methyl groups. Methionines residues have been used as probes to identify the NMR spectra corresponding to intermediates states and active species of the functional cycle. Thanks to theses probes, it has been possible to follow in real time the structural rearrangements corresponding to the different conformations of the chaperonin during its functional cycle. The second part deals with the characterization of the interaction between the chaperonin and an unfolded protein. Observation of the stabilization of the unfolded protein by the chaperonin allowed to identify the holdase activity of the chaperonin. Using a clever combination of a differential methyl labeling and optimized NMR spectroscopy for large assemblies, it has been possible to follow the refolding of the unfolded protein by the chaperonin and the effects of the unfolded protein on the functional cycle of the chaperonin in action.

Es gliomes sont des tumeurs cérébrales associées à une mortalité élevée. Le glioblastome multiforme (GBM) est la forme la plus fréquente des tumeurs cérébrales primaires. Malgré une prise en charge thérapeutique optimale constituée d'une chirurgie, d'une radiochimiothérapie concomitante et d'une chimiothérapie adjuvante, la survie médiane est de 15 mois. Ceci s'explique surtout par le potentiel infiltratif de ces tumeurs. Il est donc difficile de réaliser une exérèse chirurgicale totale, ce qui entraine une récidive quasi-systématique avec l'apparition de chimiorésistance. Ces phénomènes de résistances associés à une importante toxicité des molécules cytotoxiques mettent en évidence l'importance de rechercher de nouvelles stratégies thérapeutiques. Parmi ces dernières, les anticorps monoclonaux thérapeutiques sont très prometteurs, leurs actions ciblées limitent la toxicité au niveau du tissu sain. Cependant ces nouvelles thérapies manquent cruellement de suivi. L'apparition d'effets secondaires graves remet en cause leur intérêt. C'est pourquoi ces nouvelles thérapies, bien qu'efficaces, doivent être contrôlées par l'intermédiaire de biomarqueurs compagnons ce qui permettrait une meilleure efficience de la molécule. Le bevacizumab en est un bon exemple, de par une pharmacocinétique interindividuelle variable (de 11 à 50 jours) et une absence d'adaptation de la posologie on constate l'apparition d'effets secondaires (phlébite, hémorragie) qui entrainent l'arrêt du traitement. Or, ces effets secondaires pourraient être limités par un simple suivi de la concentration sérique de bevacizumab. De plus, dans le cas particulier des GBM, la présence de la barrière hémato-encéphalique (BHE) nécessite de développer de nouvelles stratégies pour favoriser une meilleure biodistrubution de molécules au niveau de la tumeur cérébrale. De ce fait, nous avons étudié l'efficacité d'un contournement de la BHE mécanique par une administration localisée directement dans la tumeur. Et dans cette étude préclinique, une amélioration significative de la médiane de survie des animaux ayant eu un traitement par CED (Convection Enhanced Delivery) par rapport à une administration intrapéritonéale. Enfin, dans le but de proposer une technique innovante de criblage de biomarqueurs compagnons, nous avons mis en place une stratégie innovante de marquage isotopique in vivo afin d'étudier la dynamique du protéome tumoral en réponse au traitement. Cette stratégie, déjà validée, est en cours de transfert chez l'homme dans l'étude du métabolisme des GBM. / Gliomas are brain tumors associated with important mortality. Glioblastoma multiforme (GBM) is the most frequent of primary brain tumors. Despite an optimal therapeutic management consists that includes surgery, radiotherapy plus concomitant and adjuvant chemotherapy, the median survival is 15 months. This, is mainly due to the presence of infiltrative tumor cells that hamper total surgical excision, and leads to relapse with the emergence of drug resistance. This highlights the importance of seeking new therapeutic strategies.Of these, therapeutic monoclonal antibodies are very promising. Their targeted actions limit the toxicity to healthy tissue. However, these new therapies are desperately short of monitoring. The appearance of serious side effects is a present challenge to their use. In consequences, these targeted therapies, even effective, have to be controlled via companion’s biomarkers that would provide better monitoring of the molecule. Bevacizumab is a good illustration for the existence of interindividual pharmacokinetic variability (11 to 50 days). In addition to its effect on the therapy efficiency, this inte variability must be also considered for side effects (phlebitis, hemorrhage) that lead to failure of treatment. However, these side effects could be limited by a simple monitoring of serum concentration of bevacizumab.Moreover, in the specific case of GBM, the action to the blood-brain barrier (BBB) requires the development of new strategies to promote a better bio-distribution of molecules in the brain tumor. Therefore, we investigated the effectiveness of a mechanical bypass of BBB in experimental brain tumors by a localized administration directly in the tumor. In this preclinical study, a significant improvement in median survival of animals treated with convection-enhanced delivery (CED) versus intraperitoneal administration was demonstrated.Finally, in order to offer an innovative technique of companion’s biomarkers screening, we have implemented an isotope labeling in vivo in order to study the dynamics of the proteome in tumor response to treatment. This strategy has already been released and is being transferred in humans in the study of the metabolism of GBM.

Made available in DSpace on 2014-06-11T19:26:13Z (GMT). No. of bitstreams: 0 Previous issue date: 2007-10-05Bitstream added on 2014-06-13T20:14:55Z : No. of bitstreams: 1 fracalossi_cp_me_rcla.pdf: 1652239 bytes, checksum: 44f88bcded0aee03b826c091bf22a576 (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Neste trabalho foram desenvolvidos estudos termocronológicos e hidroquímicos próximos às cidades de Limeira e Americana, centro do estado de São Paulo. A aplicação da análise dos isótopos de urânio nas águas subterrâneas do aqüífero Itararé permitiu o reconhecimento do aumento de 234U a partir das áreas topograficamente mais elevadas para áreas topograficamente mais baixas, ou seja, a razão de atividade 234U/238U aumentou a partir das áreas de recarga. O uso do método de análises de traços de fissão em apatita registrou através das histórias térmicas, um apagamento total dos traços de fissão com início de retenção dos traços a partir de 118 Ma para a amostra TF-856 e 97 Ma para a amostra TF-858. Estas idades registram o primeiro período de soerguimento da área com início de geração das paleoáreas de recarga. Posteriormente, entre o Cretáceo Superior e o Paleoceno, um período de aquecimento foi evidenciado e mais tarde, a partir do Eoceno até os dias atuais a área passa por uma nova fase de soerguimento. Este trabalho introduz a utilização do método de análise por traços de fissão no reconhecimento de altos estruturais para a caracterização de paleoáreas de recarga. / For this research were done thermochronological and hydrochemical studies close to Limeira and Americana cities, central region of São Paulo State. Using the U-isotopes analysis in groundwater from Itararé aquifer was identified a larger quantity of U234 from higher to lower topographic areas, which means that the 234U/238U activity rate got higher from recharge areas. The application of apatites fission-track analysis registered, through thermal histories, the total resetting of the fission-tracks from 118 Ma for the sample TF-856 and 97 Ma for the sample TF-858. These ages register the first uplift time of this area which caused the origin of the paleo-recharge areas. Between Upper Cretaceous and Paleocene a heating period was registered and afterwards, from Eocene to the present time, is evidenced that the area gets a new uplift phase. This work suggests the use of fission-tracks analysis for the recognition of structural height and its consequence to the paleo-recharge areas.

Le nitrate, produit de la fin de chaîne de réaction des oxydes d’azotes de l’atmosphère (NOx = NO +NO2), est l’un des ions le plus abondant de la neige et de la glace polaire. Ses rapports isotopiques stables (δ18O, δ15N et Δ17O) ont été abondamment utilisés pour contraindre ses sources et les chemins réactionnels. De plus, le nitrate archivé dans les carottes de glace profondes peut apporter de nouvelles contraintes sur les conditions climatiques passées. Cependant, le dépôt de nitrate dans les régions polaires à faible accumulation est réversible en raison des processus post-dépôts, compliquant l’interprétation des enregistrements. Actuellement, il existe des enregistrements de nitrate issus de carottes de glace profonds couvrant de l’information climatique sur plusieurs milliers d’années dont leur interprétation dépend d’une quantification précise ces phénomènes post-dépôts. Nous avons étudié expérimentalement le transfert d’excès-17O de l’ozone durant la réaction en phase gaz de NO2 + O3  NO3 + O2, qui est une réaction importante de la chimie nocturne de formation du nitrate. De cette étude nous avons déterminé la fonction de transfert du 17O donnée par : ∆17O(O3*) = (1.23 ± 0.19) × ∆17O(O3)bulk + (9.02 ± 0.99). Nous avons aussi évalué la distribution intramoléculaire des isotopes de l’oxygène de l’ozone et observé que l’excès d’enrichissement résidait de manière prépondérante sur les atomes terminaux de l’ozone. Ces résultats auront une implication importante sur la compréhension de la formation du nitrate via les mécanismes d’oxydation des précurseurs NOx. L’impact de la photolyse sur les concentrations et les compositions isotopiques stables du nitrate est étudié dans ce travail de thèse sur la base d’étude de laboratoire et de terrain. Une étude de laboratoire a été conduite en irradiant de la neige naturelle de Dôme C avec une lampe UV à xénon et en utilisant différents filtres UV (280 nm, 305 nm et 320 nm). Sur la base des mesures des rapports isotopiques de l’oxygène et de l’azote, la dépendance aux longueurs d’onde des fractionnements isotopiques a été déterminée. En conséquence, en présence de lumière UV de haute énergie, le fractionnement isotopique est décalé vers des valeurs moins négatives et vice versa. Sur la base des fractionnements isotopiques obtenus en laboratoire, nous avons dérivé un décalage apparent de la valeur du zéro point d’énergie (ZPE) qui apporte une meilleure contrainte sur la section efficace d’absorption du 15NO3-. Ce décalage apparent est obtenu en minimisant les écarts entre les observations et les fractionnements isotopiques calculés basés sur un modèle de décalage ZPE, modèle qui inclut outre le décalage ZPE, le changement des largeurs, de l’asymétrie et de l’amplitude des sections efficaces d’absorption lors de la substitution isotopique. Nous avons validé le nouveau ZPE apparent en conduisant une étude de terrain à Dôme C, Antarctique. Dans cette étude, un dispositif expérimental a été construit sur le site et l’effet du rayonnement solaire UV sur la photolyse du nitrate de la neige investigué. Cette étude était basée sur la comparaison de deux puits remplis par de la neige soufflée homogénéisée dont l’un des deux puits n’était pas soumis aux rayonnements UV. Le fractionnement isotopique de 15N pour la neige exposée aux UV (-67.9 ± 12 ‰) est en bon accord avec le modèle de décalage ZPE estimé au cours de ce travail de thèse (-55.4 ‰). Ces valeurs sont aussi dans la gamme des fractionnements isotopiques apparents observée précédemment au Dôme C. Nous pensons que l’inclusion des ces nouvelles connaissances dans un modèle prédisant l’enrichissement du 15N dans les carottes de glace permettra une interprétation quantitative de l’information préservée dans la glace. / Nitrate, the end product of oxidation of atmospheric NOX (= NO + NO2), is one of the most abundant anions present in polar snow and ice. Its stable isotope ratios (δ18O, δ15N and Δ17O) have been widely used to constrain its sources and oxidation pathways. In addition, the nitrate archived in deep ice cores may be an important metric to constrain past climatic conditions. However, deposition of nitrate in polar regions with low snow accumulation is reversible due to post-depositional processes, and interpretation of this record is complicated. Currently, there exist deep ice core records of nitrate encompassing climatic information of millennial time scales, and their interpretation relies on careful quantification of post-depositional effects. We have experimentally studied the 17O-excess transfer from ozone during the gas phase NO2 + O3 → NO3 + O2 reaction, which is an important nighttime nitrate formation pathway. From this study, we have determined the ∆17O transfer function given by: ∆17O(O3*) = (1.23 ± 0.19) × ∆17O(O3)bulk + (9.02 ± 0.99). We have also evaluated the intramolecular oxygen isotope distribution of ozone and have observed the excess enrichment resides predominantly on the terminal oxygen atoms of ozone. The findings from this study will have an important implication for understanding nitrate formation pathways via different NOX oxidation mechanisms. The impact of photolysis on the amount and stable isotope enrichments of nitrate is investigated in this PhD study based on laboratory and field experiments. A laboratory study was conducted by irradiating a natural snow from Dome C with a Xe UV lamp and a selection of UV-filters (280 nm, 305 nm and 320 nm). Based on the oxygen and nitrogen isotope ratio measurements, wavelength dependent isotopic fractionations were determined. Accordingly, in the presence of high-energy UV light, isotopic fractionation is shifted towards less negative values and the reverse for lower energy UV photons. Based the isotopic fractionations obtained in the laboratory study, we derived an apparent ZPE-shift value, which better constrains the absorption cross-section of 15NO3-. This apparent shift is derived from the best fit between the experimental observations and calculated fractionations based on existing ZPE-shift model and it includes actual ZPE-shift and changes in width, asymmetry and amplitude in absorption cross-section during isotopic substitution. We have validated the newly derived apparent ZPE-shift by conducting a field study at Dome C, Antarctica. In this study, an experimental setup was built on-site and the effect of solar UV photolysis on snow nitrate was investigated. This study was based on a comparison of two snow pits filled with locally drifted snow and by allowing/blocking the solar UV. The 15N fractionation for the UV exposed samples (-67.9 ± 12 ‰) was in fairly good agreement with the ZPE-shift model estimate from this study (-55.4 ‰). These values are also within the range of apparent isotopic fractionation observed at Dome C in previous studies. Further calculations to better constrain the absorption cross-section of 15NO3- with the ZPE-shift are underway, and we propose that the newly derived apparent ZPE-shift value should be used in future studies. We believe that incorporating these new findings in models predicting the enrichments of 15N nitrate in ice cores will allow a quantitative interpretation of the information preserved in ice.

Made available in DSpace on 2014-06-11T19:27:28Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-06-23Bitstream added on 2014-06-13T20:56:38Z : No. of bitstreams: 1 martins_mb_me_botfmvz.pdf: 732603 bytes, checksum: aaa29421580edf9cbe7e5d86e1091b6f (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Universidade Estadual Paulista (UNESP) / Este trabalho objetivou avaliar o turnover e a meia-vida do carbono nas fezes e sangue de ovelhas alimentadas com plantas C3 e C4, pela técnica dos isótopos estáveis. Oito ovelhas da raça Santa Inês, após um período de adaptação de 45 dias recebendo 50% de feno de alfafa e 50% de silagem de milho, foram distribuídas ao acaso em dois tratamentos: o primeiro consistiu de animais que receberam feno de alfafa (C3-FA) e o segundo, dos animais que receberam apenas silagem de milho (C4-SM). Para mensurar o turnover de carbono (substituição isotópica) nas fezes e sangue em determinado intervalo de tempo, foi utilizada a função exponencial do tempo. Apenas os valores isotópicos das fezes atingiram o patamar de equilíbrio, indicando valores de meia-vida de 1,2 e 1,0 dias para os tratamentos C3-FA e C4-SM, respectivamente. Já no sangue, o tempo de coleta dos dados (104 dias) foi insuficiente para encontrar o patamar de equilíbrio isotópico, indicando uma troca de carbono lenta. De acordo com os resultados deste estudo, pode-se concluir que o sangue apresenta turnover lento indicando o sinal isotópico de dietas antigas; e as fezes, turnover rápido, indicadas para refletir dietas recentes, próximas da fase de avaliação / The aim of this work was to evaluate the carbon turnover and half-life on feces and blood sheep, fed on C3 and C4 plants, using the stable isotopes technique. Eight Santa Ines sheep, after 45 days as adjustment period receiving 50% of alfalfa hay and 50% of corn silage, were randomly assigned to two treatments: the first one the animals fed on alfalfa hay (C3-FA) and the second one the animals fed on only corn silage (C4-SM). The time exponential function was used to measure the carbon turnover (isotope substitution) on feces and blood in a certain period of time. Only the isotope feces values reached the plateau value, indicating half-life of 1.2 and 1.0 days for C3-FA and C4-SM treatment, respectively. The data collection time (104 days) for blood was not enough to find a plateau isotope, indicating a slow carbon exchange. So we can infer that the blood has a slow turnover, indicating isotopic signal of ancient diets; and the feces showed a fast turnover, being used to reflect recent diet, next to the evaluation period

Neste trabalho foi estabelecido um procedimento para determinação da razão isotópica 238U/235U em amostras de UF6, utilizando-se um espectrômetro de massas quadrupolar com ionização por impacto eletrônico e detecção de íons por copo de Faraday ou multiplicador de elétrons. Para tanto, o espectrômetro foi otimizado, determinando-se os parâmetros para a fonte de íons que proporcionassem a maior intensidade de corrente iônica, mantendo o pico de forma arredondada, para a massa correspondente ao isótopo mais abundante; a resolução que reduzisse os efeitos não lineares e o número de ciclos analíticos que reduzisse a incerteza nos resultados. O processo de medição foi caracterizado quanto: aos efeitos de discriminação de massa, linearidade e efeito memória. A discriminação de massas mostrou ser linearmente dependente da pressão da amostra no tanque de expansão nas faixas de 0,15 a 0,30 mbar e de 0,30 a 0,40 mbar. O espectrômetro mostrou-se linear na medição de razões isotópicas entre 0,005 e 0,045. Os fatores de memória para a fonte de íons e para o sistema de introdução são, respectivamente, 1,000 ± 0,001 e 1,003 ± 0,003; o primeiro pode ser desprezado e o segundo eliminado por procedimentos de lavagem do sistema de introdução. O trabalho apresenta, em sua parte final, um roteiro para as análises de amostras de UF6 e a determinação das incertezas nos resultados. / In the present work a procedure for determination of the isotopic ratio 238U/235U in UF6 samples was established using a quadrupole mass spectrometer with ionization by electron impact and ion detection by Faraday cup or electron multiplier. For this, the following items were optimized in the spectrometer: the parameters in the íon source that provided the most intense peak, with good shape, for the corresponding mass of the most abundant isotope; the resolution that reduced the non linear effects and the number of analytic cycles that reduced the uncertainty in the results. The measurement process was characterized with respect to the effects of mass discrimination, linearity and memory effect. The mass discrimination showed to be linearly dependent of the sample pressure in the batch volume, for the pressure ranges from 0.15 to 0.30 mbar and from 0.30 to 0.40 mbar. The spectrometer was shown linear in the measurement of isotopic ratios between 0.005 and 0.045. The memory factor for the íon source and for the introduction system were, respectively, 1.000 ± 0.001 and 1.003 ± 0.003; the first one can be ignored, the second one can be eliminated by washing the batch volume with the new sample. A methodology for routine analysis of UF6 samples and the determination of the uncertainties were set up in details as well.

Made available in DSpace on 2016-06-02T19:29:24Z (GMT). No. of bitstreams: 1 3085.pdf: 11800699 bytes, checksum: 71c066e8e0a2f17d9129aaf2bec7145c (MD5) Previous issue date: 2010-04-24 / Records of isotopic and elemental carbon and nitrogen and pollen in lake sediments and soils have been used for studies of Quaternary paleoecology worldwide, including in the Amazon at specific sites, such as the region of Carajas, Lake Pata and Region Porto Velho in Rondonia state making it necessary to register in the central southern region. We collected two cores in the Lagoa Jabuti site and a core on the Site Três Coqueiros in the floodplain of the Teles Pires river in northern Mato Grosso state. The cores were analyzed for elemental and isotopic nitrogen and carbon (% C, % N, 13C, 15N and C/N), and palynology and radiometric dating by 14C via AMS. Was also used samples of Quaternary megafauna and elements of material culture. From the analysis carried out it appears that southern Amazon in the Mato Grosso there were no significant ecological changes during the study period, which is around 5,500 years B.P., except for the registration of a relatively sharp change in carbon isotope values for about 2,700 years BP. The pollen analysis of the sediment of Jabuti showed the predominance of elements on forest herb/fern coinciding with data from botanical surveys conducted in the area in which stand families Fabaceae, Arecaceae, Euphorbiaceae, Malvaceae, Combretaceae, Melastomataceae, Annonaceae, among the trees; Cyperaceae , Asteraceae, Chenopodiaceae, Poaceae, Achantaceae and Amaranthaceae between herbs and Polygonaceae, Cyatheaceae and Asplenium among the ferns. The megafauna considered in the paper presented by ESR beyond the age covered by the project and analyzed the material culture (ceramics) revealed that from the earliest moments of occupation (about 1,300 years BP) the ecological conditions of the region have not changed, although they have been registered large gaps in regional occupation that can be interpreted as a crisis in the supply of natural resources necessary for survival in the region. / Registros de dados isotópicos e elementares de carbono e nitrogênio e palinológicos em sedimentos lacustres e solos têm sido utilizados para estudos da paleoecologia do Quaternário em todo mundo, inclusive na Amazônia em sítios específicos, a exemplo da região de Carajás, Lagoa da Pata e região de Porto Velho no estado de Rondônia fazendo-se necessário o registro na região centro meridional da região. Foram coletados dois testemunhos de sondagem na Lagoa Jabuti e um testemunho no Sítio Três Coqueiros na planície de inundação do rio Teles Pires no norte de Mato Grosso. Os testemunhos foram analisados elementar e isotopicamente para nitrogênio e carbono (%C, %N, 13C, 15N e C/N), além de palinologia e datação radiométrica pelo 14C via AMS. Foram ainda utilizadas amostras da megafauna quaternária e elementos da cultura material. A partir das análises executadas, especialmente δ13C (-222 a - ) verifica-se que na Amazônia Meridional matogrossense não ocorreram significativas mudanças ecológicas no período estudado, que está em torno dos 5.500 anos, exceto pelo registro de uma alteração relativamente acentuada nos valores isotópicos de carbono há cerca de 2.700 anos A.P. A análise palinológica dos sedimentos da Lagoa Jabuti evidenciaram a predominância de elementos florestais sobre ervas/pteridófita coincidindo com os dados de levantamentos botânicos efetuados na região em que sobressaem famílias Fabaceae, Arecaceae, Euphorbiaceae, Malvaceae, Combretaceae, Melastomataceae, Annonaceae, entre as arbóreas; Cyperaceae, Asteraceae, Chenopodiaceae, Poaceae, Achantaceae e Amaranthaceae entre as ervas e Polygonaceae, Asplenium e Cyatheaceae entre as pteridófitas. A megafauna considerada no trabalho apresentou pelo ESR idade além da abrangida pelo projeto e a cultura material analisada (cerâmica) revelou que desde os primeiros momentos de ocupação (cerca de 1.300 anos A.P.) as condições ecológicas da região não se alteraram, ainda que tenham sido registrados grandes hiatos na ocupação regional que podem ser interpretados como crises no fornecimento de recursos naturais fundamentais para a sobrevivência na região.