Orientador: Arthur Bernardes Cecílio Filho / Resumo: O manejo eficiente de nutrientes é crucial para atingir alta produtividade de frutos. Resultados da análise do tecido são comumente interpretados usando faixas críticas de concentração de nutrientes (CNCR) e Sistema Integrado de Diagnose e Recomendação (DRIS) em culturas de laranja. No entanto, ambos os métodos ignoram as propriedades inerentes à classe dos dados composicionais, não considerando adequadamente as interações de nutrientes e a influência varietal na composição nutricional da planta. Portanto, ferramentas eficazes de modelagem são necessárias para corrigir vieses e incorporar efeitos genéticos na avaliação do estado nutricional. O objetivo deste estudo foi desenvolver uma abordagem diagnóstica precisa para avaliar o estado nutricional de variedades de copa de laranjeira (Citrus sinensis), usando a análise composicional dos dados e algoritmos de inteligência artificial. Foram coletadas 716 amostras foliares de ramos frutíferos em pomares comerciais de laranjeiras não irrigadas (“Valência”, “Hamlin”, “Pera”, “Natal”, “Valencia Americana” e “Westin”) distribuídos pelo estado de São Paulo (Brasil), analisadas as concentrações de N, S, P, K, Ca, Mg, B, Cu, Zn, Mn e Fe, e avaliadas as produções de frutos. Balanços de nutrientes foram computados como relações-log isométricas (ilr). Análises discriminantes dos valores de ilr diferenciaram os perfis de nutrientes das variedades de copa, indicando composições nutricionais específicas. A acurácia diagnóstica dos balanços de... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Efficient nutrient management is crucial to attain high fruit productivity. Results of tissue analysis are commonly interpreted using critical nutrient concentration ranges (CNCR) and Diagnosis and Recommendation Integrated System (DRIS) on orange crops. Nevertheless, both methods ignore the inherent properties of compositional data class, not accounting adequately for nutrient interactions and varietal influence on plant ionome. Therefore, effective modeling tools are needed to rectify biases and incorporate genetic effects on nutrient composition. The objective of this study was to develop an accurate diagnostic approach to evaluate the nutritional status across orange (Citrus sinensis) canopy varieties using compositional data analysis and machine learning algorithms. We collected 716 foliar samples from fruit-bearing shoots in plots of non-irrigated commercial orange orchards (“Valencia”, “Hamlin”, “Pera”, “Natal”, “Valencia Americana” and “Westin”) distributed across São Paulo state (Brazil), analyzed N, S, P, K, Ca, Mg, B, Cu, Zn, Mn and Fe, and measured fruit yields. Sound nutrient balances were computed as isometric log-ratios (ilr). Discriminant analysis of ilr values differentiated the nutrient profiles of canopy varieties, indicating plant-specific ionomes. Diagnostic accuracy of nutrient balances reached 88% about cutoff yield of 60 Mg ha-1 using ilrs and a k-nearest neighbors classification, allowing the development of reliable nutritional standards at high fruit... (Complete abstract click electronic access below) / Doutor

La plupart des études sur l’influence de la température sur la production des spermatozoïdes portent en grande partie sur les vertébrés. Néanmoins, les invertébrés constituent la majorité de la biodiversité terrestre animale, sont également plus sensibles à ces variations de température. Les travaux réalisés au cours de cette thèse ont porté sur la compréhension des capacités de reproduction, et sur l’influence d’une augmentation de température sur les fonctions mâles chez Nasonia vitripennis, un hyménoptère parasitoïde. Ce travail de thèse m’a permis de confirmer que chez cette espèce, la spermatogenèse était synchronisée et de décrire pour la première fois, un système de stockage intermédiaire des spermatozoïdes entre les testicules et les vésicules séminales. De plus, j’ai pu mettre en évidence que la spermatogénèse était sensible à une augmentation de température pendant le développement, altérant le sexe ratio de la descendance par des modifications d’allocations des sexes par les femelles. Ces résultats apportent de nouvelles connaissances sur la fertilité mâle chez cette espèce et démontrent la sensibilité de la spermatogenèse à la température. / Many studies on the impact of the temperature on spermatogenesis have largely focused on vertebrates. Nevertheless, invertebrates constitute the vast majority of terrestrial biodiversity, and are especially vulnerable to variations of temperatures. The studies realized during my thesis are focused on understanding male reproductive capacities and effects of heat stress on male fertility in a parasitic wasp Nasonia vitripennis. This work allowed to confirm that spermatogenesis was synchronized, and to describe for the first time a system of spermatozoa regulation between testis and seminal vesicles. Moreover, I was able to demonstrate that spermatogenesis was sensible to temperature variation during male development, and the offspring sex ratio was altered by modifications of sex allocation. These findings open the way to the description of male fertility in this species, and show the sensitivity of spermatogenesis to temperature variation.

Esse trabalho buscou avaliar a possibilidade de utilização do glicerol como fonte de carbono para a desnitrificação conjunta à remoção biológica de fósforo de um efluente sintético em um reator de fluxo contínuo submetido à aeração intermitente e com biomassa suspensa. O regime operacional do reator foi dividido em duas fases: a primeira visando somente a remoção de nitrato, testando diferentes relações Carbono/Nitrogênio (C/N) em Tempo de Detenção Hidráulica (TDH) de 4 horas; e a segunda visando a remoção de nitrato e fosfato com períodos de aeração e não aeração de 2 e 4 horas respectivamente, para uma relação Carbono/Fósforo de 10 ± 1. Na primeira fase operacional foram testadas 3 relações C/N, a saber: 1,2 ± 0,1; 1,5 ± 0,1 e 1,8 ± 0,2. Para a relação C/N de 1,8 ± 0,2 foi possível atingir uma maior eficiência de desnitrificação com uma maior estabilidade operacional - 91 ± 8%. Para a segunda fase de operação que apresentou relação C/N de 3,5 ± 0,2, a desnitrificação foi completa na maior parte do tempo com 99 ± 2% de eficiência de remoção de NOx (nitrato mais nitrito), indicando que a desnitrificação com glicerol é favorecida para relações C/N mais altas. Não foi evidenciado uma remoção biológica de fósforo expressiva (9 ± 12%), indicando que não houve desenvolvimento dos organismos acumuladores de fósforo (OAPs), uma vez que a liberação de fosfato durante a fase não aerada não ocorreu. Isso pode ser explicado pela falta de ácidos graxos voláteis (AGV), que seriam provenientes da degradação anaeróbia do glicerol, sendo a maior parte desse consumida na desnitrificação. Portanto, o teor de nitrato pode ter sido um fator de impedimento ao desenvolvimento dos OAPs. Pelos ensaios de microscopia óptica foi observado a presença de bactérias filamentosas semelhantes às do gênero Beggiatoa, que também podem ter consumido parte dos substratos da fermentação do glicerol. Por essas razões, sugere-se avaliar outras configurações de reatores de modo a promover uma efetiva fermentação do glicerol previamente ao sistema de remoção de fósforo. / This study aimed to evaluate the feasibility of glycerol as a carbon source for denitrification and biological phosphorus removal of a synthetic wastewater in a continuous flow reactor with suspended biomass and subjected to intermittent aeration. The reactor operation was divided in two phases: the first one aimed only at removing nitrate, testing different C/N (Carbon/Nitrogen) ratios at an HRT (Hydraulic Retention Time) of 4 hours; and the second one aimed at the removal of nitrate and phosphate. During the second phase, the reactor was subjected to periods of aeration and non-aeration of 2 and 4 hours, respectively, for a C/P (Carbon/Phosphorus) ratio of 10 ± 1. In the first operational phase, three C/N ratios were tested, as follows: 1.2 ± 0.1; 1.5 ± 0.1 and 1.8 ± 0.2. For the C/N ratio of 1.8 ± 0.2, it was possible to achieve higher denitrification efficiency with greater operational stability - 91 ± 8%. For the second operational phase, with the C/N ratio of 3.5 ± 0.2, the denitrification was complete most of the time presenting 99 ± 2% of NOx (nitrate and nitrite) removal efficiency, indicating that the denitrification with glycerol is enhanced at higher C/N ratios. The biological phosphorus removal in this phase was not significant (12 ± 9%), indicating that there was no development of Phosphorus Accumulating Organisms (PAO), since the phosphate release during the anaerobic phase did not occur. This can be explained by the lack of Volatile Fatty Acids (VFA), which would come from the anaerobic degradation of glycerol that was consumed in denitrification. Therefore, the nitrate content may have been an interfering factor to the development of PAO. The optical microscopy analysis indicated the presence of filamentous bacteria similar to the genus Beggiatoa, which can also have consumed part of the substrates from the glycerol fermentation. For these reasons, it is suggested to evaluate other reactor configurations in order to promote the effective fermentation of glycerol previously to the phosphorus removal system.

Este trabalho buscou verificar a viabilidade do uso de fermentado de glicerol como fonte externa de carbono para a remoção biológica de nutrientes em um reator de leito estruturado, submetido à aeração intermitente (LEAI). O LEAI foi alimentado com efluente de reator UASB de bancada, usado no tratamento de esgoto sanitário. O reator LEAI possuía volume total de 12,3L e, devido às hastes cilíndricas verticais de espuma de poliuretano usadas como suporte para a biomassa, o volume útil foi de 8,6 L. Inicialmente, o reator foi operado sob aeração contínua com tempo de detenção hidráulica (TDH) de 24 horas e razão de recirculação de efluente igual a 3 para desenvolvimento de biomassa nitrificante no reator. Após a eficiência de nitrificação atingir 80%, o reator passou a ser operado com TDH de 12 horas e sob aeração intermitente, mantendo-se a razão de recirculação igual a 3. Foram então realizadas 4 fases em modo contínuo sob aeração intermitente (tempo de aeração/tempo sem aeração) de 2h/1h sem glicerol, 3h/1h sem glicerol, 2h/1h com glicerol, 3h/1h com glicerol. A adição de glicerol fermentado ocorreu somente durante os períodos não aerados. Em todas as fases, a DQO média efluente ao sistema variou entre 26±8 e 59±14 mg.L-1. Em relação à remoção de nitrogênio total (como NTK), verificou-se a baixa eficiência de remoção nas fases em que não houve a adição do fermentado, atingindo 49,6±13,5% (2h/1h) e 29,2±10,1% (3h/1h). Entretanto, nas fases em que houve a inserção do glicerol, as eficiências de remoção de N-total foram superiores, obtendo-se 64,9±21,6% (2h/1h) e 69,5±11,7% (3h/1h). Não foi observada remoção de fósforo em nenhuma das fases em que o reator foi operado com alimentação contínua. A fim de verificar a eficácia do fermentado de glicerol na remoção de N e P, o sistema foi modificado para que o reator LEAI operasse em bateladas sequenciais (RSB). Nessa etapa da pesquisa, observou-se o estabelecimento da comunidade acumuladora de fósforo no sistema, obtendo-se eficiência de remoção de fósforo de 56,1±8,5%. A eficiência de remoção de nitrogênio total também aumentou, atingindo 86,2±6,2%. Concluiu-se que o fermentado do glicerol apresenta potencial significativo para uso como fonte exógena de carbono no processo de remoção de fósforo e N-total. Concluiu-se também que, embora o glicerol fermentado contenha compostos favoráveis à remoção de fósforo em reatores de leito estruturado, a alimentação contínua do reator com aeração intermitente, não promove as condições ideais para o estabelecimento de processo estável de remoção de fósforo. No entanto, a elevada eficiência de oxidação de NTK, de remoção de matéria orgânica e de desnitrificação, aliadas à baixa produção sólida, mostram que o LEAI é uma alternativa interessante em comparação às tecnologias praticadas atualmente para pós-tratamento de efluentes de reatores anaeróbios. Contudo, quando a remoção de fósforo é necessária, a operação do reator em bateladas sequenciais é a alternativa viável. / This work aimed to verify the viability of the use of fermented glycerol as an external carbon source for the nutrient biological removal in structured-bed reactor subjected to recirculation and intermittent aeration (SBRRIA). The SBRRIA was fed effluent from UASB reactor bench scale, used in the treatment of domestic sewage. The SBTTIA reactor had a total volume of 12.3L and, due to the vertical cylindrical strips of polyurethane foam used as biomass support, the useful volume was 8.6 L. Initially, the reactor was operated under continuous aeration with hydraulic retention time (HRT) of 24 hours and effluent recirculation ratio of 3 for the development of nitrifying biomass in the reactor. After the nitrification efficiency reach 80%, the reactor started to be operated at the HRT of 12 h under intermittent aeration, maintaining the recirculation ratio equal to 3. Four phases were then carried out continuously under intermittent aeration (aeration / time without aeration) of 2h/1h without glycerol, 3h/1h without glycerol, 2h/1h with glycerol, 3h/1h with glycerol. The addition of fermented glycerol occurred only during time without aeration. In all phases, the average COD effluent of the system ranged between 26±8 and 59±14 mg.L-1. Low removal efficiency of total nitrogen (as TKN) was verified in the phases without addition of the fermented glycerol, reaching 49.6±13.5% (2h/1h) and 29.2±10.1% (3h/1h). However, the efficiency of total nitrogen removal efficiency was higher when fermented glycerol was added during the non-aerated period, attaining 64.9±21.6% (2h/1h) and 69.5±11.7% (3h/1h). No phosphorus removal was observed in any of the previous phases in which the reactor was operated under continuous feeding. In order to verify the feasibility of fermented glycerol in the removal of N and P, the system was modified so that the LEAI reactor operated in sequential batch mode (SRB). At this stage of the research, the establishment of the phosphorus accumulating community in the system was observed and phosphorus removal efficiency attained 56.1±8.5%. The efficiency of total nitrogen removal also increased up to 86.2±6.2%. It was concluded that the fermented glycerol presents significant potential for use as an exogenous carbon source in the process of phosphorus and nitrogen removal. It can be also concluded that fixed bed reactors can remove phosphorus from wastewaters using fermented glycerol presenting compounds favorable to the development of phosphorus accumulating microorganisms (PAO). However, reactors subjected to continuous feeding and intermittent aeration do not promote good conditions for the establishment of stable phosphorus removal process. Nevertheless, the high efficiency of TKN oxidation, organic matter removal and denitrification, coupled with low solid production, show that SBRRIA is an interesting alternative for the post-treatment of anaerobic reactor effluents. However, when phosphorus removal is required, sequential batch reactor operation is the viable alternative.

L’évaluation de biomarqueurs et de thérapies innovantes pour la maladie d’Alzheimer (MA) souffre de la mauvaise compréhension des phases initiales de la maladie mais également du manque de modèles animaux pertinents et proches de la physiopathologie humaine. La majorité des modèles rongeurs disponibles reproduisent en seulement quelques mois les lésions classiques de la MA telles que les plaques amyloïdes et les dégénérescences neurofibrillaires (DNF), alors que leur apparition prend des années chez l’Homme. L’objectif de mon travail de doctorat a été de développer une nouvelle stratégie de modélisation des phases précoces de la MA sans surexpression majeure de transgène. Pour cela, nous avons utilisé le co-transfert des gènes humains APPSL et PS1M146L à l’aide de vecteurs viraux dans l’hippocampe de souris et de rats de 8 semaines. Nous avons caractérisé ces modèles et montré une production de peptides, comme le betaCTF ou l’abeta?42 issus du clivage de l’APP, similaire à ce que l’on observe dans l’hippocampe de patients atteints de la MA. Nous avons également montré une hyperphosphorylation de Tau et une défaillance synaptique caractérisée par une diminution des niveaux de PSD-95 et GLT-1 ainsi que par une augmentation du courant tonique glutamatergique. Ces modifications ont enfin été associées à des défauts comportementaux. Mes résultats suggèrent que de nombreux évènements apparaissent bien avant la formation des plaques amyloïdes ou des DNFs et conduisent à une perturbation de la synapse et à l’apparition précoce de défauts comportementaux. Nous disposons donc d’outils relevants quant à la compréhension des premiers stades de la MA qui permettront à la fois de tester de nouveaux composés médicaments sur ces modèles à large fenêtre thérapeutique, et de découvrir de nouveaux biomarqueurs précoces dans le plasma et le liquide cérébro-spinal. / Evaluation of biomarkers and new innovative therapies for Alzheimer's disease (AD) suffers from a misunderstanding of early phases and lack of appropriate animal models close to the human physiopathology. Most available rodent models reproduce hallmarks of AD such as amyloid plaques and neurofibrillary tangles in a few months, while it takes many years to be achieved in human. My PhD work consisted to develop a new modelling strategy of AD early phases without major overexpression of transgenes. To do so, we used gene transfer of human APPSL and PS1M146L using viral vectors injection in the hippocampus of 8 weeks old mice and rats. We characterized these models and showed peptides production, such as betaCTF and abeta42 from APP processing, similar to what is observed in AD patients hippocampi. We also highlighted a hyperphosphorylation of Tau followed by a synaptic failure characterized by a decrease of PSD-95 and GLT-1 levels and by an increase of the tonic current mediated by glutamate. These changes have been finally associated with behavioral deficits. My results suggest that many events appear well before the formation of amyloid plaques or tangles and lead to the disruption of the synapse and the early onset of behavioral defects. Thus, we now have relevant tools to understand the early stages of AD, which will allow us to test new drug compounds on these models with a wide therapeutic window and discover new early biomarkers in plasma and cerebrospinal fluid.

The main aim of the diploma thesis is to perform a financial analysis of Komerční banka, a. s. in sufficient time, to find out its capital adequacy and, in case of deficiencies, to propose measures that would lead to improvement of the situation. To meet this objective, horizontal and vertical balance sheet items, profit and loss account were prepared. In conclusion, the financial situation of the bank was assessed on the basis of selected ratio indicators. The results of all partial analyzes were correlated with the results of three competing banks and the entire banking sector for higher relevance.

[pt] O neoconstitucionalismo presente no Estado Contemporâneo - marcado pela diversidade, multiculturalismo e complexidade - teve como marco as atrocidades cometidas durante a Segunda Guerra Mundial e se caracteriza por fatores como a expansão dos direitos humanos e fundamentais e a normatização das Constituições Democráticas que apresentam em sua essência uma elevada carga axiológica e principiológica, conferindo caráter mais aberto ao texto legal, colocando o indivíduo no centro o ordenamento jurídico. Esse cenário resultou na reformulação não somente do conceito de jurisdição, mas de todo o direito processual, rompendo com o tecnicismo inerente a esse ramo do direito. Ao superar o clássico modelo subsuntivo e adotar o método interpretativo deliberativo de aplicação do direito, o neoconstitucionalismo fortaleceu o Poder Judiciário e conferiu maior liberdade aos juízes na interpretação e ressignificação da norma diante do caso concreto, conformando-a com a realidade sócio-políticojurídica. Esse movimento de resgate das teorias hermenêuticas aqueceu a discussão sobre segurança jurídica, uma vez que potencializou a divergência de entendimento jurisprudencial nos países adeptos ao sistema de civil law, como é o caso do Brasil. A adoção da teoria dos precedentes judiciais vinculantes - inerente ao sistema jurídico do common law - no Brasil, apresenta-se como instrumento de uniformização da jurisprudência capaz de garantir a segurança jurídica ao elevar o grau de previsibilidade, estabilidade e confiabilidade do direito, permitindo aos cidadãos planejar suas ações e prever seus resultados. / [en] The neoconstitutionalism present in the Contemporary State - marked by diversity, multiculturalism and complexity - had as a landmark atrocities committed during the Second World War and is characterized by factors such as the expansion of human and fundamental rights and the regulation of the Democratic Constitutions which present in their being an axiological and principled high load , giving more open to legal text character by placing the individual at the center of the legal system. This scenario resulted in reshaping not only the concept of jurisdiction, but of the entire procedural law, breaking the technicality inherent in this field of law. By overcoming the classical model and adopting the interpretive-deliberative method of applying the law, neoconstitutionalism strengthened the judiciary and gave greater freedom to judges in interpretation and reframing the norm face the case, conforming with the legal socio-political reality. This movement of redemption of hermeneutical theories heated discussion about legal security, once it enhanced the divergence of legal understanding in the civil law system countries, such as Brazil. The adoption of the theory of binding judicial precedent - inherent in the legal system of common law - in Brazil, presents itself as an instrument of unification of jurisprudence able to guarantee legal certainty by raising the degree of predictability, stability and reliability of the law, allowing citizens plan their actions and predict their results.

Made available in DSpace on 2016-04-25T18:39:39Z (GMT). No. of bitstreams: 1 Cibele de Paula Deis.pdf: 672256 bytes, checksum: 63dd609334b89d8b2e6b3f76d3f9de9a (MD5) Previous issue date: 2011-05-23 / PricewaterhouseCoopers Auditores Independentes / The purpose of this study is to analyze the performance of insurance companies operating in auto lines, during the period from 1999 to 2008. Based on the analysis of the combined and broad-based combined ratios, as well as other correlated indices (claims ratio and ratios of selling and administrative expenses), it was possible to ascertain the level of dependence on financial gains required to obtain positive results. The study was limited to insurance companies operating in auto lines, which is Brazil's most popular type of insurance and, in this context, 18 large, medium and small insurance companies were analyzed based on their financial statements. The performance of insurance companies linked to banks, as well as that of the independent companies was examined. The results of the study revealed that, during the period from 1999 to 2008, financial gains contributed from 10.19% to 17.52% to improving the operating efficiency of the insurance companies under analysis and to maintaining, for the whole period, the broad-based combined ratios below 100%. At the same time, the average combined ratios determined varied from 122.91% to 98.33%. Only in 2006 and 2007, did the sample under analysis present operating efficiency. Moreover, the insurance companies presented high operating costs, especially for claims. In a comparison between the bank-linked insurance companies and the independent insurance companies, it was noted that, on average, the selling and administrative expenses of insurance companies which use a bank branch network for distributing their products were lower than those of the independent companies comprising the sample. During the period from 2003 to 2007, the large-sized insurance companies not associated to banks revealed a gradual improvement in operating efficiency, due to the significant decrease in the claims ratio of the portfolio and a partial reduction in administrative expenses. Considering that competition is expected to become even tougher, it follows that the insurance companies will need to focus on reducing costs and improving their operating controls in order to reduce their dependence on financial results and promote the continuity of their business / O objetivo deste trabalho é analisar o desempenho operacional de seguradoras que operam no ramo de Automóveis, no período de 1999 a 2008. A partir da análise dos índices combinado e combinado ampliado, bem como dos demais índices correlatos (sinistralidade e das despesas de comercialização e administrativa) foi possível verificar o nível de dependência dos ganhos financeiros para obtenção de resultados positivos. A pesquisa foi limitada às seguradoras que atuam no ramo de Automóveis, que é o seguro mais popular no país, e, nesse contexto, foram estudadas as 18 maiores seguradoras de grande, médio e pequeno porte, tomando por base as demonstrações contábeis. Verificou-se, também, o desempenho das seguradoras ligadas a Bancos e as Independentes. Os resultados da pesquisa evidenciaram que no período de 1999 a 2008, os ganhos financeiros contribuíram de 10,19% a 17,52% para melhoria da eficiência operacional das seguradoras estudadas e, fazendo com que durante todo o período os índices combinados ampliados ficassem inferiores a 100%. Por sua vez, os índices combinados médios apurados variaram de 122,91% a 98,33%. A amostra estudada apresentou eficiência operacional, somente em relação aos exercícios de 2006 e 2007. Além disso, as seguradoras apresentaram elevados custos operacionais, especialmente, com sinistros. Na comparação das seguradoras ligadas a Bancos e independentes, observou-se que, na média, as despesas de comercialização e administrativas das seguradoras que utilizam a rede de agência dos Bancos para distribuição de seus produtos foram inferiores as demais. No período de 2003 a 2007, as seguradoras de grande porte não ligadas a Bancos mostraram uma melhoria gradual na eficiência operacional, devido à redução significativa da sinistralidade da carteira e parcialmente das despesas administrativas. Considerando que a concorrência tende a continuar ser cada vez mais acirrada, conclui-se que as seguradoras necessitam focar na redução dos custos e controles operacionais, a fim de reduzir sua dependência dos resultados financeiros e a continuidade do seu negócio

Le soufre est un composant volatil important des magmas qui présente différents états d'oxydation en fonction des conditions d’oxydoréduction et de la phase dans laquelle il se trouve : dans le liquide silicaté, il est typiquement dissous comme S⁶⁺ et/ou S²⁻ , dans la phase gazeuse il se trouve principalement comme SO₂ (S⁴⁺ ) et H₂S (S²⁻). L’Etna, pour lequel les conditions d’oxydoréduction sont faiblement contraintes, est utilisée comme cas d’étude pour examiner le comportement du soufre dans les magmas basaltiques hydratés pendant la différenciation et le dégazage. Cette recherche combine l'étude des inclusions vitreuses avec une étude expérimentale en conditions magmatiques sur la solubilité du S dans les basaltes alcalins hydratés.Les résultats expérimentaux suggèrent l’important contrôle de la ƒO₂ sur la teneur en S dans les magmas hydratés de l’Etna, et le partage du S entre les phases fluid and liquid. Les inclusions vitreuses ont été piégées à différentes profondeurs à l'intérieur du système magmatique. Elles décrivent une tendance continue de différenciation, marquée par une cristallisation fractionnée, à partir de la composition picritique (FS) vers le basalte plus récent dégazé (2013). Le contenu en S dans le liquide de l'Etna est extrêmement variable et atteint 4150 ppm dans les inclusions vitreuses les plus primitives. Les spectres XANES Fe³⁺/ΣFe des certaines inclusions vitreuses donnent des rapports Fe³⁺/ΣFe généralement décroissants à partir du liquide le plus primitif (FS) jusqu’au plus évolué (2013). Les simulations effectué par le logiciel MELTS confirme que la diminution du rapport Fe³⁺/ΣFe est principalement due au processus de différenciation magmatique, renforcé par le dégazage du S à ƒO₂ < NNO + 1. Cette réduction du magma provoque à son tour la diminution de la solubilité du S dans les basaltes hydratés de l’Etna, et peut constituer un éventuel activateur de l’exsolution du S, à l’origine de l’important dégazage du S observé au cours des dernières décennies à l’Etna. / Sulfur is an important volatile component of magmas that presents different oxidation states, depending on the redox conditions and on the phase of occurrence: in silicate melts it is typically dissolved as S⁶⁺ and/or S²⁻ , in the gas phase it occurs principally as SO₂ (S⁴⁺ ) and H₂S (S²⁻). Mount Etna, in which magmatic redox conditions are poorly constrained, is used as a case study to investigate sulfur behavior in hydrous basaltic magmas during magma differentiation and degassing. This research integrates the study of natural olivine-hosted melt inclusions with an experimental study on S solubility in hydrous alkali basalts at magmatic conditions.Experimental results suggest the important control of ƒO₂ on the S abundance in Etnean hydrous magma and its partitioning between fluid and melt phases. Melt inclusions were entrapped at different depths inside the magmatic system (up to ~ 18 km, below crater level). They delineate a continuous differentiation trend, marked by fractional crystallization, from the picritic basalt (FS) toward the most evolved and degassed (2013) basalt. S content in Etnean melt is extremely variable and reaches 4150 ppm in the primitive melt inclusions. XANES Fe³⁺/ΣFe spectra in some glass inclusions, resulted in the generally decreasing of Fe³⁺/ΣFe ratios from the most primitive (FS) to the most evolved (2013) melts. MELTS software confirms that the Fe³⁺/ΣFe decrease is due principally to the melt differentiation process, enhanced to the S degassing at ƒO₂ < NNO+1. Magma reduction, in turn, induces the decrease of the sulfur solubility in the hydrous Etnean basalt, as well as of the sulfide saturation, and may constitute a possible enhancer of S exsolution, triggering the important S degassing observed in the last decades in Mt. Etna.

Submitted by Danilo Ricardo Yamane (danilo_yamane@yahoo.com.br) on 2019-01-28T17:15:40Z No. of bitstreams: 1 Tese Yamane (2018).pdf: 2814108 bytes, checksum: f2e102e5809427e8d3d26d0a59971542 (MD5) / Approved for entry into archive by Tatiana Camila Gricio (tatiana.gricio@unesp.br) on 2019-01-28T17:32:17Z (GMT) No. of bitstreams: 1 yamane_dr_dr_jabo.pdf: 2814108 bytes, checksum: f2e102e5809427e8d3d26d0a59971542 (MD5) / Made available in DSpace on 2019-01-28T17:32:17Z (GMT). No. of bitstreams: 1 yamane_dr_dr_jabo.pdf: 2814108 bytes, checksum: f2e102e5809427e8d3d26d0a59971542 (MD5) Previous issue date: 2018-11-29 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O manejo eficiente de nutrientes é crucial para atingir alta produtividade de frutos. Resultados da análise do tecido são comumente interpretados usando faixas críticas de concentração de nutrientes (CNCR) e Sistema Integrado de Diagnose e Recomendação (DRIS) em culturas de laranja. No entanto, ambos os métodos ignoram as propriedades inerentes à classe dos dados composicionais, não considerando adequadamente as interações de nutrientes e a influência varietal na composição nutricional da planta. Portanto, ferramentas eficazes de modelagem são necessárias para corrigir vieses e incorporar efeitos genéticos na avaliação do estado nutricional. O objetivo deste estudo foi desenvolver uma abordagem diagnóstica precisa para avaliar o estado nutricional de variedades de copa de laranjeira (Citrus sinensis), usando a análise composicional dos dados e algoritmos de inteligência artificial. Foram coletadas 716 amostras foliares de ramos frutíferos em pomares comerciais de laranjeiras não irrigadas (“Valência”, “Hamlin”, “Pera”, “Natal”, “Valencia Americana” e “Westin”) distribuídos pelo estado de São Paulo (Brasil), analisadas as concentrações de N, S, P, K, Ca, Mg, B, Cu, Zn, Mn e Fe, e avaliadas as produções de frutos. Balanços de nutrientes foram computados como relações-log isométricas (ilr). Análises discriminantes dos valores de ilr diferenciaram os perfis de nutrientes das variedades de copa, indicando composições nutricionais específicas. A acurácia diagnóstica dos balanços de nutrientes atingiu 88% com a produtividade de corte correspondente a 60 t ha-1, utilizando-se ilrs e o algoritmo de classificação knn, o que possibilitou o desenvolvimento de padrões nutricionais confiáveis para a obtenção de elevado nível de produtividade de frutos. Os citricultores do estado de São Paulo devem adotar o conceito de balanços de nutrientes, onde grupos de nutrientes estão equilibrados de maneira ideal. Fornecer mais Ca através de calcário ou gesso, reduzir as aplicações de fertilizantes P e K, e aumentar a fertilização de B via solo pode reequilibrar os balanços [Mg | Ca], [Ca, Mg | K], [P | N, S], [K, Ca, Mg | N, S, P] e [B | N, S, P, K, Ca, Mg] em pomares de laranjas com produtividade inferior a 60 t ha-1. O software “CND-Citros” pode auxiliar os citricultores, engenheiros agrônomos e técnicos a diagnosticar o estado nutricional das lavouras de laranja com base no método proposto, utilizando os resultados da análise química das folhas. / Efficient nutrient management is crucial to attain high fruit productivity. Results of tissue analysis are commonly interpreted using critical nutrient concentration ranges (CNCR) and Diagnosis and Recommendation Integrated System (DRIS) on orange crops. Nevertheless, both methods ignore the inherent properties of compositional data class, not accounting adequately for nutrient interactions and varietal influence on plant ionome. Therefore, effective modeling tools are needed to rectify biases and incorporate genetic effects on nutrient composition. The objective of this study was to develop an accurate diagnostic approach to evaluate the nutritional status across orange (Citrus sinensis) canopy varieties using compositional data analysis and machine learning algorithms. We collected 716 foliar samples from fruit-bearing shoots in plots of non-irrigated commercial orange orchards (“Valencia”, “Hamlin”, “Pera”, “Natal”, “Valencia Americana” and “Westin”) distributed across São Paulo state (Brazil), analyzed N, S, P, K, Ca, Mg, B, Cu, Zn, Mn and Fe, and measured fruit yields. Sound nutrient balances were computed as isometric log-ratios (ilr). Discriminant analysis of ilr values differentiated the nutrient profiles of canopy varieties, indicating plant-specific ionomes. Diagnostic accuracy of nutrient balances reached 88% about cutoff yield of 60 Mg ha-1 using ilrs and a k-nearest neighbors classification, allowing the development of reliable nutritional standards at high fruit yield level. Citrus growers from São Paulo state should adopt the concept of yield-limiting nutrient balances, where groups of nutrients are optimally balanced. Supplying more Ca as lime or gypsum materials, reducing the P and K fertilizer applications and enhancing soil B fertilization could re-establish the [Mg | Ca], [Ca, Mg | K], [P | N, S], [K, Ca, Mg | N, S, P] and [B | N, S, P, K, Ca, Mg] balances in orange orchards yielding less than 60 Mg ha-1. The software “CND-Citros” can assist citrus growers, agronomy engineers and technicians to diagnose the nutrient status of orange crops based on the proposed method, using the results of leaf chemical analysis.